CN116711029A

CN116711029A - Photoactive compounds for vapor deposition of organic photovoltaic devices

Info

Publication number: CN116711029A
Application number: CN202180087712.XA
Authority: CN
Inventors: 奥斯丁·史密斯; 马修·E·赛克斯; 维尼特·库默; 道格拉斯·R·罗贝洛; 约翰·A·洛夫; 阿贾拉·萨弗科; 塞尔瓦姆·苏布拉马尼亚姆; 里沙·潘迪; 迈尔斯·C·巴尔
Original assignee: Ubiquitous Energy Inc
Current assignee: Ubiquitous Energy Inc
Priority date: 2020-11-04
Filing date: 2021-11-04
Publication date: 2023-09-05
Also published as: CN117062821A

Abstract

Photoactive compounds are disclosed. The disclosed compounds may exhibit molecular structural elements that tend to increase the evaporability or volatility of the compound, for example, by using conformationally constrained side groups instead of free-rotating side groups or indandione moieties instead of dicyandiamide indanone moieties to include geometric core disruption. The disclosed photoactive compounds include those compounds having imine-bridged linkages that can convert optical properties to more redshifted absorption than with olefin-bridged linkages. The disclosed photoactive compounds are useful in organic photovoltaic devices, such as visible light transparent or opaque photovoltaic devices.

Description

Photoactive compounds for vapor deposition of organic photovoltaic devices

Cross Reference to Related Applications

The present application claims the benefits and priorities of U.S. provisional application Ser. No. 63/109,722, U.S. provisional application Ser. No. 63/140,744, U.S. provisional application Ser. No. 63/141,387, U.S. provisional application Ser. No. 63/758, U.S. provisional application Ser. No. 63/141,390, and U.S. provisional application Ser. No. 63/275,311, and U.S. provisional application Ser. No. 63/390, and U.S. provisional application Ser. No. 63/275,311, U.S. provisional application Ser. No. 63/390, and U.S. 11/3 of 2021, all of which are both filed on 11 and 22 of 2021, respectively, as filed on 11 and 4 of year 2020.

Technical Field

The present application relates generally to the field of optically active materials and devices, and more particularly to photovoltaic materials for organic photovoltaic devices, and methods of manufacturing photovoltaic devices.

Background

The surface area necessary to harness solar energy remains a significant obstacle to counter the consumption of non-renewable energy sources. For this reason, low cost, transparent, organic Photovoltaic (OPV) devices that can be integrated into window panes for homes, skyscrapers, and automobiles are desirable. For example, glazings used in automobiles and buildings typically transmit 70-80% and 55-90% of the visible spectrum, respectively, for example light having a wavelength of about 450 to 650 nanometers (nm). Limited mechanical flexibility, high module cost, and more importantly, band-like absorption of inorganic semiconductors limit their potential application in transparent solar cells.

In contrast, the optical characteristics of organic and molecular semiconductors result in a highly structured absorption spectrum, with absorption minima and maxima, which are distinct from the band absorption of their inorganic counterparts. However, there are a variety of organic and molecular semiconductors, but many of them exhibit strong absorption in the visible spectrum and are therefore not the best choice for glazing-based photovoltaic devices.

Fullerene electron acceptors, e.g. C ₆₀ And C ₇₀ Historically used in different organic photovoltaic solar cell structures. However, there is interest in developing NFA (non-fullerene receptors) due to overlapping absorption in the visible region and cost and purification issues. One type of NFA is based on the molecule ITIC (3, 9-bis (2-methylene- (3- (1, 1-dicyanomethylene) -indanone)) -5,5,11,11-tetrakis (4-hexylbenzene)Radical) -dithioeno [2,3-d:2',3' -d ] ']-s-indeno [1,2-b:5,6-b ]']Dithiophene (3, 9-bis (2-methyl- (3- (1, 1-dicyanoxyphenyl) -indanone)) -5,5,11,11-tetrakis (4-hexylphenyl) -dithiino [2,3-d:2',3' -d ] ']-s-indaceno[1,2-b:5,6-b’]dithiophene), which molecule comprises indenodithia [3,2-b ]]Thiophene core (IT) with four 4-hexylphenyl groups and capped with 2- (3-oxo-2, 3-indan-1-ylidene) malononitrile (INCN) groups. Such and related ITIC-type receptors are generally considered high performance NFA materials, but they cannot be deposited by physical vapor deposition. All known examples of devices comprising ITIC-type receptors are produced by solution-based processing. Solution-based devices containing ITIC-type materials have created world recording capabilities for opaque organic photovoltaics, but large-scale manufacturing using solution-based processing techniques presents challenges.

Disclosure of Invention

Described herein are materials, methods, and systems relating to organic photovoltaic devices, in some cases particularly suitable for use in visible light transparent organic photovoltaic devices, as well as partially transparent organic photovoltaic devices and opaque organic photovoltaic devices. More specifically, the present specification provides photoactive compounds that are useful, for example, as acceptor molecules or donor molecules, and methods and systems incorporating the disclosed compounds as photoactive materials for photovoltaic devices.

The disclosed photoactive compounds include those having the formula A-D-A, A-pi-D-A or A-pi-D-pi-A, wherein A is an electron acceptor moiety, pi is a pi-bridging moiety, and D is an electron donor moiety. In some cases, the photoactive compound may have the formula A-D or A-pi-D. Variants of the A, D and pi moieties are described herein, but these moieties can be selected to provide absorption and electrochemical properties suitable for use as electron donor molecules or electron acceptors in organic photovoltaic devices. The disclosed photoactive compounds may be suitable for purification using sublimation and deposition onto a surface using a vacuum deposition process (e.g., vacuum thermal evaporation). For example, their sublimation temperature may be lower than the temperature at which they thermally decompose. A. The nature, molecular weight and structure of the D and pi moieties can affect the volatility of the photoactive compounds in a variety of ways, as described in further detail below.

In some embodiments, the D moiety in the photoactive compound may comprise a fused aromatic ring structure, e.g., comprising one or more five-membered rings and/or one or more six-membered rings, wherein the rings are optionally carbocyclic or heterocyclic, e.g., comprising one or more heteroatoms, such as O, S, se, N, si or Ge. The D moiety may also include one or more pendent groups, which may be referred to as a Z group or a Z moiety. These Z groups may be bonded to carbon atoms in the fused ring structure, and optionally multiple Z groups are bonded to the same carbon atom, which may be a quaternary center, such as quaternary C, si or Ge. Exemplary Z groups may be alkyl, alkenyl, or phenyl, which may be substituted or unsubstituted. In some cases, two Z groups may form a ring.

In some embodiments, the Z groups may be referred to as planarity breaking moieties or breaking moieties, in that these groups may extend out of the plane of the fused aromatic ring structure and include structures that lock the atoms of the Z groups in place out of the plane in conformational or spatial relation to the fused aromatic ring structure. Such an out-of-plane conformation may disrupt the crystal packing structure, e.g., alter the melting, sublimation, or vapor pressure related properties of the photoactive compound. In some cases, the disruption may make the photoactive compound more suitable for deposition using a physical vapor deposition process or purification by sublimation. In other cases, the Z group may not significantly disrupt the planar configuration of the fused aromatic ring structure.

In some embodiments, moiety a in the photoactive compound may include indanone, indandione, indanthione, indandithione, dicyanomethylene indanone, or bis (dicyanomethylene) indane. In some cases, indandione (indacene) may be referred to as indanedione (indanedione). In some cases, indanthione may be referred to as thioindanone. In some cases, indan dithione (indanithone) may be referred to as indene dithione (indanedithione). In some cases, dicyanomethyleneindanone may be referred to as malononitrile indanone. In some cases, the bis (dicyanomethylene) indane may be referred to as a dipropylene dinitrile indane. Other a moieties may also or alternatively be included in the photoactive compound, for example a moiety comprising five-and/or six-membered rings, which may include one or more heteroatoms, such as thiophenes or other heterocycles. In other embodiments, part a may comprise a vinyl cyano ester linked compound.

Alternatively, the a moiety may be bonded to the D moiety or pi moiety by a carbon-carbon bond (carbon linkage), or include a nitrogen atom and be bonded to the D moiety or pi moiety by a nitrogen-carbon bond (imine linkage). The use of an imine-linked moiety a can alter the spectral properties of the photoactive compound, for example, causing a red shift compared to the same compound using a carbon linkage rather than an imine linkage.

In some embodiments, the pi moiety may include an aromatic or heteroaromatic structure including one or more five-membered rings and/or one or more six-membered rings having a double radical structure, thereby providing a connection between the a and D moieties. Examples of pi moieties may include, but are not limited to, thiophenes and fused thiophenes.

As described above, the photoactive compound may be suitable for deposition using vacuum deposition techniques such as vacuum thermal evaporation. In some cases, the molecular weight of the photoactive compound may affect the volatility of the compound, as compounds having very high molecular weights may eventually thermally decompose before evaporating or sublimating. In some embodiments, the upper molecular weight limit of the photoactive compound may be about 1200 atomic mass units.

Also described herein are photovoltaic devices incorporating the photoactive compounds, methods of making the photoactive compounds, and methods of making photovoltaic devices incorporating the photoactive compounds.

These and other examples, embodiments, and aspects of the invention, along with many advantages and features, are described in more detail in connection with the following description and accompanying drawings.

Drawings

Fig. 1 provides a schematic representation of a photoactive compound according to some embodiments.

Fig. 2 provides a schematic illustration of another photoactive compound according to some embodiments.

Fig. 3A is a simplified schematic diagram illustrating a visible light transparent photovoltaic device according to some embodiments.

Fig. 3B provides an overview of various configurations of photoactive layers in a visible light transparent photovoltaic device according to some embodiments.

Fig. 4 is a simplified graph illustrating solar spectrum, human eye sensitivity, and absorption as a function of wavelength for an exemplary transparent photovoltaic device.

Fig. 5 is a simplified energy level diagram of a visible light transparent photovoltaic device according to some embodiments.

Diagrams illustrating exemplary absorption profiles for different electron acceptor and electron donor configurations (which may include photoactive layers) are provided in fig. 6A, 6B, 6C, and 6D.

Fig. 7 provides an overview of a method of manufacturing a visible light transparent photovoltaic device according to some embodiments.

FIG. 8 provides a synthetic scheme for preparing exemplary compounds that can be used to prepare various core-disrupted photoactive compounds.

FIG. 9 provides a synthetic scheme for preparing various exemplary core-disrupted photoactive compounds.

FIG. 10 provides a synthetic scheme for preparing various exemplary core-disrupted photoactive compounds.

FIG. 11 provides a synthetic scheme for preparing exemplary core-disrupted photoactive compounds.

FIG. 12 provides a synthetic scheme for preparing exemplary core-disrupted photoactive compounds.

FIG. 13 provides a synthetic scheme for preparing exemplary core-disrupted photoactive compounds.

FIG. 14 provides a synthetic scheme for preparing exemplary compounds that can be used to prepare various photoactive compounds.

FIG. 15 provides a synthetic scheme for preparing various exemplary photoactive compounds.

FIG. 16 provides a synthetic scheme for preparing exemplary indandione containing photoactive compounds.

FIG. 17 provides a synthetic scheme for preparing exemplary core-disrupted indandione-containing photoactive compounds.

FIG. 18 provides a synthetic scheme for preparing exemplary core-disrupted indandione-containing photoactive compounds.

FIG. 19 provides a synthetic scheme for preparing exemplary core-disrupted indandione-containing photoactive compounds.

FIG. 20 provides a synthetic scheme for preparing exemplary core-disrupted photoactive compounds.

FIG. 21 provides a synthetic scheme for preparing exemplary compounds that can be used to prepare various photoactive compounds.

FIG. 22 provides a synthetic scheme for preparing various exemplary photoactive compounds.

FIG. 23 provides a synthetic scheme for preparing exemplary photoactive compounds.

FIG. 24 provides a synthetic scheme for preparing exemplary compounds useful for preparing various core-disrupted photoactive compounds including quaternary silicon centers.

FIG. 25 provides a synthetic scheme for preparing various exemplary core-disrupted photoactive compounds.

FIG. 26 provides a synthetic scheme for preparing exemplary photoactive compounds.

FIG. 27 provides a synthetic scheme for preparing exemplary indandione containing photoactive compounds.

FIG. 28 provides a synthetic scheme for preparing exemplary indandione-containing photoactive compounds.

FIG. 29 provides a synthetic scheme for preparing exemplary indandione containing photoactive compounds.

FIG. 30 provides a synthetic scheme for preparing exemplary indandione containing photoactive compounds.

FIG. 31 provides a synthetic scheme for preparing exemplary indandione containing photoactive compounds.

FIG. 32 provides a synthetic scheme for preparing exemplary indandione-containing photoactive compounds.

FIG. 33 provides a synthetic scheme for preparing exemplary indandione containing photoactive compounds.

FIG. 34 provides a synthetic scheme for preparing exemplary indandione-containing photoactive compounds.

Fig. 35 provides a synthetic scheme illustrating the preparation of exemplary photoactive compounds according to some embodiments.

Fig. 36 provides a graph showing normalized absorption of exemplary photoactive compounds according to some embodiments.

Fig. 37 provides a graph illustrating sublimation yields of exemplary photoactive compounds according to some embodiments.

Fig. 38 provides the absorption coefficients of exemplary photoactive compounds used to construct transparent photovoltaic devices.

Fig. 39A, 39B, 39C, and 39D provide schematic diagrams of exemplary photovoltaic device structures.

Fig. 40A provides a graph of current density versus voltage curves for the photovoltaic devices shown in fig. 39A-39D.

Fig. 40B provides external quantum efficiency graphs for the photovoltaic devices shown in fig. 39A-39D.

Fig. 40C provides a graph showing the transmission spectra of the photovoltaic devices shown in fig. 39A-39D.

Detailed Description

The present disclosure relates to photoactive compounds useful as electron acceptor compounds or electron donor compounds, photovoltaic devices incorporating the disclosed photoactive compounds as photoactive materials, and methods of making and using photovoltaic devices. The disclosed photoactive compounds have properties such as relatively low molecular weight, relatively high vapor pressure, etc., allowing the compounds to be purified and/or deposited using vapor phase techniques such as sublimation, vacuum thermal evaporation, and physical vapor deposition. Furthermore, the photoactive compounds exhibit strong absorption, allowing for use in organic photovoltaic devices. In some cases, photoactive compounds exhibit strong light absorption in the near infrared and/or ultraviolet region and weak light absorption in the visible region, which allows their use in visible transparent photovoltaic devices. In other cases, photoactive compounds can be used in transparent and opaque photovoltaic devices.

The disclosed photoactive compounds include compounds having specific characteristics that may provide advantages for use as electron acceptors, but may also be used as electron donors in some cases, depending on the pairing of photoactive compounds with other compounds in an organic photovoltaic device. The disclosed compounds may exhibit a molecular structure in which different moieties or substructures are bonded to each other, such as an electron donor moiety (D), an electron acceptor moiety (a), and a pi-bridging moiety (pi). The components may be arranged in any suitable arrangement to form the photoactive compound. Furthermore, each of the different components may include certain structural/compositional features that may affect various properties of the photoactive compound, such as band gap, enthalpy of sublimation, sublimation temperature, or crystal bulk density, for example.

For example, some of the disclosed compounds may exhibit a structure of formula A-D-A or A-D or have a structure of formula A-D-A or A-D. FIG. 1 provides a schematic representation of a photoactive compound 100 having an A-D-A structure. Fig. 1 shows a first electron acceptor portion 105, a second electron acceptor portion 110, and an electron donor portion 115 between the first electron acceptor portion 105 and the second electron acceptor portion 110. In the case where the photoactive compound 100 has an a-D structure, the second electron acceptor moiety 110 may not be present and the electron donor moiety 115 may include a small group, such as a hydrogen atom, alkyl group, alkylene group, or the like, otherwise, the second electron acceptor moiety 110 may be present at the location of the small group. Alternatively, the first electron acceptor moiety 105 and the second electron acceptor moiety 110 may be the same. Alternatively, the first electron acceptor moiety 105 and the second electron acceptor moiety 110 may be different.

In some cases, pi-bridging moieties may be located between the a and D moieties such that the disclosed compounds may exhibit an a-pi-D-A, A-pi-D-pi-a or a-pi-D structure or have the formula a-pi-D-A, A-pi-D-pi-a or a-pi-D. FIG. 2 provides a schematic representation of a photoactive compound 200 having the structure A-pi-D-pi-A. Fig. 2 shows a first electron acceptor moiety 205, a second electron acceptor moiety 210, an electron donor moiety 215, a first pi-bridging moiety 220, and a second pi-bridging moiety 225. As shown, a first pi-bridging portion 220 is located between the first electron acceptor portion 205 and the electron donor portion 215, and a second pi-bridging portion 225 is located between the electron donor portion 215 and the second electron acceptor portion 210. In the case where the photoactive compound 200 has an a-pi-D-a structure, the second pi-bridging moiety 225 may not be present. In the case where the photoactive compound 200 has an a-pi-D structure, the second electron acceptor moiety 210 may not be present and the electron donor moiety 215 may include a small group, such as a hydrogen atom, an alkyl group, an alkylene group, or the like, otherwise, the second electron acceptor moiety 210 may be present at the location of the small group. In some embodiments, the second pi-bridging moiety 225 may also be absent. Alternatively, the first electron acceptor moiety 205 and the second electron acceptor moiety 210 may be the same. Alternatively, the first electron acceptor moiety 205 and the second electron acceptor moiety 210 may be different. Alternatively, the first pi-bridging moiety 220 and the second pi-bridging moiety 225 can be the same. Alternatively, the first pi-bridged moiety 220 and the second pi-bridged moiety 225 may be different.

As shown, electron donor portions 115 and 215 can have various subcomponents, which can contribute to certain features. For example, electron donor moiety 115 or 215 can include a central core 130 or 230 and a pendent group 135 or 235. In some electron donors, the central core 130 or 230 may have or exhibit an electron rich planar molecular structure, for example, in which one or more carbon atoms and optionally one or more heteroatoms are arranged in a plane. In some cases, the central core 130 or 230 may comprise an aromatic or heteroaromatic structure that optionally includes one or more five-membered rings, one or more six-membered rings, or one or more five-membered rings and one or more six-membered rings, e.g., in a fused ring configuration.

The pendant groups 135 or 235 may include any suitable organic group, optionally including one or more heteroatoms. In some cases, the pendent groups 135 or 235 may be in any molecular arrangement, such as by including a bond that allows free rotation. However, in other cases, the atoms making up the pendent groups 135 or 235 may have a bonding configuration that locks the atoms in a particular geometry. For example, the pendent groups 135 or 235 may be or include one or more planarity-disrupting moieties that are conformally locked in a configuration out of the plane of the central core 130 or 230. Without wishing to be bound by any theory, the inclusion of a pendent group as a planarity-disrupting moiety may affect the ability of the molecules of photoactive compound 100 or 200 to form closely packed crystals in the bulk, as the planarity-disrupting moiety may provide a molecular structure that is forced into a monolithic non-planar molecular geometry. For example, such a configuration may result in a decrease in the bulk density of crystals. Other properties, such as melting enthalpy, evaporation enthalpy or sublimation enthalpy, melting temperature, boiling temperature or sublimation temperature, may also be affected. Thus, by including a planarity-disrupting portion in the chemical structure, the photoactive compound 100 or 200 may be more suitable for purification using a sublimation process or for deposition by a vapor deposition process such as vacuum thermal evaporation. In some cases, the use of a planarity disrupting moiety may increase the evaporation capacity of the photoactive compound, for example to a higher level than a comparable photoactive compound having the same electron acceptor moiety, pi-bridging moiety (if present), and central core but including side groups that are not planarity disrupting moieties but have the same or about the same molecular weight.

The electron donor groups 105, 110, 205, or 220 may have various subcomponents, which may contribute to certain features. For example, in some cases, one or more of the electron acceptor groups 105, 110, 205, or 220 may comprise a particular composition, such as indandione, aryl-substituted indandione, indanthione, aryl-substituted indanthione, indandithione, or aryl-substituted indandithione. These compositions may be contrasted with other electron acceptor groups that may be used for some photoactive molecules, such as dicyandiamide ketone or bis (dicyandiamide) indanone groups containing dicyanovinyl or = C (CN) ₂ A group. However, the process is not limited to the above-described process, such configuration is not limiting and some electron acceptor groups may include indandione aryl substituted indandiones, indanthiones, and methods of making and using the same,Aryl substituted indanethiones, indandithiones, aryl substituted indandithiones, dicyan methylene indanones, or bis (dicyan methylene) indane groups or other electron acceptor groups. In certain specific cases of photoactive compounds having two a components, one a may comprise a dicyanovinyl-containing group and the other a may comprise indandione, aryl-substituted indandione, indanthione, aryl-substituted indanthione, indandithione, or aryl-substituted indandithione. Photoactive compounds incorporating one or more indandione, aryl-substituted indandione, indanthione, aryl-substituted indanthione, indandithione, aryl-substituted indandithione groups as electron acceptor groups may be more suitable for purification by sublimation or more suitable for vapor deposition, for example, using thermal evaporation techniques, than comparable photoactive compounds containing only dicyanomethyleneindanone or bis (dicyanomethylene) indane groups. For example, in some cases, the use of indandione, indanthione, or indandithione groups as electron acceptor groups may increase the volatility of the photoactive compound, e.g., to a higher level than a comparable photoactive compound having the same pi-bridging moiety (if present) and central core but including dicyandiamide indanone or bis (dicyandiamide) indane groups instead of indandione, indandithione, or indandithione groups. In some cases, even substitution of indandione, indanthione or indandithione groups with one dicyandiamide indanone or bis (dicyandiamide) indanone group can result in a significant increase in volatility.

As another example, the electron acceptor group 105, 110, 205, or 220 may include a specific linking structure at the point where the electron acceptor group 105, 110, 205, or 220 is bonded to the electron donor group 115 or 215 or pi-bridging group 220 or 225. For example, in some cases, the electron acceptor group 105, 110, 205, or 220 may comprise an imine bond = N-as a linking group, where a single bond corresponds to a bond with an adjacent a or pi group and a double bond corresponds to a bond with another portion of the electron acceptor group. In other cases, the electron acceptor group 105, 110, 205, or 220 may comprise an olefinic bond=ch-as a linking group, wherein a single bond corresponds to a bond with an adjacent a or pi group and a double bond corresponds to a bond with another portion of the electron acceptor group. The inclusion of imine linkages may be used to alter the bandgap or absorption maximum of the photoactive compound 100 or 200. For example, in some cases, inclusion of an imine bond may result in a red shift in the bandgap or red shift in the absorption maximum of the photoactive compound as compared to a photoactive compound having otherwise the same structure but including an olefinic bond instead of an imine bond. The preparation of photoactive compounds containing imine linkages may require a different synthetic route than that used to prepare photoactive compounds that do not contain imine linkages.

In some embodiments, very high molecular weights may be undesirable, such as about 1200amu or higher, about 1150amu or higher, about 1100amu or higher, about 1050amu or higher, about 1000amu or higher, about 950amu or higher, about 900amu or higher, or between 900amu and 2000amu or subranges thereof, for purification and use of the disclosed photoactive compounds. Some compounds with very high molecular weights may have limited volatility, while useful methods of purifying and using photoactive compounds may employ methods based on evaporation or sublimation. Furthermore, photoactive compounds may be deposited as part of a photovoltaic device using thermal evaporation techniques, while very high molecular weight compounds may be difficult to deposit using thermal evaporation. In various embodiments, the photoactive compounds described herein have a molecular weight of 200amu to 1200amu, less than or about 1150amu, less than or about 1100amu, less than or about 1050amu, less than or about 1000amu, less than or about 950amu, less than or about 900amu, less than or about 850amu, less than or about 800amu, less than or about 750amu, less than or about 700amu, less than or about 650amu, less than or about 600amu, less than or about 550amu, less than or about 500amu, less than or about 450amu, less than or about 400amu, less than or about 350amu, less than or about 300amu, less than or about 250amu, or less than or about 200amu.

To achieve the desired optical properties, photoactive compounds may exhibit a molecular electron structure in which photons of light are absorbed, resulting in lifting electrons to higher molecular orbitals whose energy difference matches that of the absorbed photons, which may result in the generation of electron-hole pairs or excitons that may subsequently separate into different electrons and holes, for example, at interfaces with other materials. Compounds that exhibit extended aromaticity or extended conjugation may be beneficial because compounds that have extended aromaticity or extended conjugation may exhibit electron absorption with energies that match the energies of near infrared, visible, and/or ultraviolet photons. In addition to conjugation and aromaticity, the absorption properties can also be adjusted by including heteroatoms (e.g., oxygen, nitrogen or sulfur atoms) in the organic structure of the visible light transparent photoactive compound.

Generally, terms and phrases used herein have art-recognized meanings known to those skilled in the art, and can be found with reference to standard text, journal references, and contexts. The following definitions are provided to clarify their specific use in the context of the present invention.

As used herein, "maximum absorption intensity" refers to the maximum absorption value in a particular spectral region, such as the ultraviolet band (e.g., 200nm to 450nm or 280nm to 450 nm), visible band (e.g., 450nm to 650 nm), or near infrared band (e.g., 650nm to 1400 nm) of a particular molecule. In some examples, the maximum absorption intensity may correspond to an absorption characteristic of a local maximum or an absolute maximum, such as an absorption band or peak absorption intensity, and may be referred to as peak absorption. In some examples, the maximum absorption intensity in a particular band may not correspond to a local maximum or an absolute maximum, but may correspond to a maximum absorption value in a particular band. For example, such a configuration may occur when the absorption features span multiple bands (e.g., visible and near infrared) and the absorption values of the absorption features that occur in one band are less than the absorption values that occur in an adjacent band, such as when the peak of the absorption feature is in the near infrared band but the tail of the absorption feature extends into the visible band. In some examples, the photoactive compounds described herein can have an absorption peak at wavelengths greater than about 650 nanometers (e.g., at near infrared), and the magnitude of the absorption peak of the photoactive compound can be greater than the absorption of the photoactive compound at any wavelength between about 450 and 650 nanometers.

In various embodiments, the disclosed compositions or compounds are isolated or purified. Alternatively, the isolated or purified compound is at least partially isolated or purified, as understood in the art. In some examples, the chemical purity of the disclosed compositions or compounds is 80% pure, optionally 90% pure for some applications, optionally 95% pure for some applications, optionally 99% pure for some applications, optionally 99.9% pure for some applications, optionally 99.99% pure for some applications, and optionally 99.999% pure for some applications. Purification of the disclosed compositions or compounds can be performed using any desired technique. Purification by chromatography, vacuum sublimation and/or crystallization may be a particularly useful technique.

The compounds disclosed herein optionally comprise one or more ionizable groups. The ionizable groups include groups from which protons can be removed (e.g., -COOH) or groups to which protons can be added (e.g., amines) and groups that can be quaternized (e.g., amines). All possible ionic forms of such molecules and salts thereof are intended to be included solely in the disclosure herein. With respect to salts of the compounds described herein, it is to be understood that a variety of available counterions can be selected that are suitable for preparing salts for a given application. In particular applications, the selection of a given anion or cation to prepare a salt may result in an increase or decrease in the solubility of the salt.

The disclosed compounds optionally contain one or more chiral centers. Thus, the present disclosure includes racemic mixtures, diastereomers, enantiomers, tautomers, and mixtures enriched in one or more stereoisomers. The disclosed compounds including chiral centers include racemic forms of the compounds, as well as individual enantiomers and non-racemic mixtures thereof.

As used herein, the terms "group" and "moiety" may refer to a functional group of a compound. The groups of the disclosed compounds refer to atoms or collections of atoms that are part of the compounds. The groups of the disclosed compounds may be attached to other atoms of the compounds by one or more covalent bonds. Groups may also be characterized in terms of their valency. The present disclosure includes groups characterized as monovalent, divalent, trivalent, etc. states. Alternatively, the term "substituent" may be used interchangeably with the terms "group" and "moiety". Groups may also be characterized in terms of their ability to provide or receive electrons, and in some embodiments such characterization may refer to the relative properties of the groups that provide or receive electrons as compared to other groups.

As is conventional and well known in the art, hydrogen atoms in the formulae disclosed herein are not always explicitly shown, e.g., hydrogen atoms bonded to carbon atoms of aliphatic, aromatic, alicyclic, carbocyclic and/or heterocyclic rings are not always explicitly shown in the formulae. Structures provided herein, for example in the context of describing any particular and structure, are intended to convey the chemical makeup of the disclosed compounds of the methods and compositions. It should be understood that the structures provided do not represent the specific positions of the atoms and the bond angles between the atoms of these compounds. As used herein, a wavy line at the end of a bond in a structure or formula represents the location where a given moiety is attached or attachable to another moiety. For example, the wavy line in section A may be paired with a wavy line in section D or pi to form section A-D or section A-pi. In some cases, the wavy line in part D may correspond to a hydrogen atom. For example, for a-D or a-pi-D compounds, some of the D moieties described herein are shown with two wavy lines, one of which may be attached to a hydrogen atom.

As used herein, the terms "alkylene" and "alkylene group" are used synonymously and refer to a divalent group derived from an alkyl group as defined herein. The present disclosure includes compounds having one or more alkylene groups. The alkylene groups in some compounds act as linking groups and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₁ -C ₂₀ Alkylene, C ₁ -C ₁₀ Alkylene or C ₁ -C ₅ An alkylene group.

As used herein, the terms "cycloalkylene" and "cycloalkylene group" are used synonymously and refer to compounds derived from the groups as defined hereinDivalent radicals of cycloalkyl radicals. The present disclosure includes compounds having one or more cycloalkylene groups. The cycloalkylene group in some compounds acts as a linking group and/or a spacer group. The disclosed compounds optionally include substituted and/or unsubstituted C ₃ -C ₂₀ Cycloalkylene, C ₃ -C ₁₀ Cycloalkylene or C ₃ -C ₅ Cycloalkylene radicals.

As used herein, the terms "arylene" and "arylene group" are used synonymously and refer to a divalent group derived from an aryl group as defined herein. The present disclosure includes compounds having one or more arylene groups. In some examples, arylene is a divalent group derived from an aryl group by removing a hydrogen atom from two ring carbon atoms of the aryl ring of the aryl group. Arylene groups in some compounds act as linking groups and/or spacer groups. Arylene groups in some compounds act as chromophores, fluorophores, aromatic antennas, dyes, and/or imaging groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₅ -C ₃₀ Arylene group, C ₅ -C ₂₀ Arylene or C ₅ -C ₁₀ Arylene groups.

As used herein, the terms "heteroarylene" and "heteroarylene group" are used synonymously and refer to a divalent group derived from a heteroaryl group as defined herein. The present disclosure includes compounds having one or more heteroarylene groups. In some examples, a heteroarylene group is a divalent group derived from a heteroaryl group by removing a hydrogen atom from a carbon atom or a nitrogen atom within the two rings of the heteroaryl ring or the aromatic ring. The heteroarylene group in some compounds acts as a linking group and/or a spacer group. The heteroarylene group in some compounds acts as a chromophore, aromatic antenna, fluorophore, dye, and/or imaging group. The disclosed compounds optionally include substituted and/or unsubstituted C ₅ -C ₃₀ Heteroarylene, C ₅ -C ₂₀ Heteroarylene or C ₅ -C ₁₀ Heteroarylene group.

As used herein, the terms "alkenylene" and "alkenylene group" are used synonymously and refer to derivatives fromDivalent groups of alkenyl groups as defined herein. The present disclosure includes compounds having one or more alkenylene groups. Alkenylene groups in some compounds function as linking groups and/or spacers. The disclosed compounds optionally include substituted and/or unsubstituted C ₂ -C ₂₀ Alkenylene, C ₂ -C ₁₀ Alkenylene or C ₂ -C ₅ Alkenylene radicals.

As used herein, the terms "cycloalkenyl" and "cycloalkenyl" are used synonymously and refer to a divalent group derived from a cycloalkenyl group as defined herein. The present disclosure includes compounds having one or more cycloalkenyl groups. Cycloalkenyl groups in some compounds act as linking groups and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₃ -C ₂₀ Cycloalkenyl ene, C ₃ -C ₁₀ Cycloalkenyl ene or C ₃ -C ₅ A cycloalkenylene group.

As used herein, the terms "alkynylene" and "alkynylene group" are used synonymously and refer to a divalent group derived from an alkynyl group as defined herein. The present disclosure includes compounds having one or more alkynylene groups. Alkynylene groups in some compounds function as linking groups and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₂ -C ₂₀ Alkynylene, C ₂ -C ₁₀ Alkynylene or C ₂ -C ₅ Alkynylene groups.

As used herein, the term "halogen" refers to a halogen group, such as fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

The term "heterocycle" refers to a ring structure in which the ring contains at least one other atom in addition to carbon. Examples of such atoms include oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, silicon, germanium, boron, aluminum, and in some cases also transition metals. Examples of heterocycles include, but are not limited to, pyrrolidinyl, piperidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl, and tetrazolyl. The atoms of the heterocycle may be bonded to a wide range of other atoms and functional groups, for example provided as substituents. Heterocycles include aromatic heterocycles and non-aromatic heterocycles.

The term "carbocycle" refers to a ring structure containing only carbon atoms in the ring. The carbon atoms of the carbocycle may be bonded to a wide range of other atoms and functional groups, for example provided as substituents. Carbocycles include aromatic carbocycles and non-aromatic carbocycles.

The term "cycloaliphatic" refers to a ring that is not an aromatic ring. Alicyclic rings include carbocycles and heterocycles.

The term "aliphatic" refers to non-aromatic hydrocarbon compounds and groups. Aliphatic groups typically include carbon atoms covalently bonded to one or more other atoms, such as carbon atoms and hydrogen atoms. However, instead of carbon atoms, aliphatic groups may include non-carbon atoms, such as oxygen atoms, nitrogen atoms, sulfur atoms, and the like. Unsubstituted aliphatic groups include only hydrogen substituents. Substituted aliphatic groups include non-hydrogen substituents, such as halogen groups and other substituents described herein. The aliphatic group may be straight chain, branched or cyclic. Aliphatic groups may be saturated, meaning that only single bonds connect adjacent carbon (or other) atoms. Aliphatic groups may be unsaturated, meaning that one or more double or triple bonds connect adjacent carbon (or other) atoms.

Alkyl groups include straight chain alkyl groups, branched chain alkyl groups, and cycloalkyl groups. Alkyl groups include alkyl groups having 1 to 30 carbon atoms. Alkyl groups include small alkyl groups having 1 to 3 carbon atoms. Alkyl groups include medium length alkyl groups having 4 to 10 carbon atoms. Alkyl groups include long chain alkyl groups having more than 10 carbon atoms, particularly long chain alkyl groups having from 10 to 30 carbon atoms. The term cycloalkyl refers in particular to alkyl groups having a ring structure, for example comprising 3 to 30 carbon atoms, optionally 3 to 20 carbon atoms and optionally 3 to 10 carbon atoms, including alkyl groups having one or more rings. Cycloalkyl includes cycloalkyl groups having a three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocyclic ring, particularly cycloalkyl groups having a three-, four-, five-, six-, or seven-membered ring. Carbocycles in cycloalkyl groups may also bear alkyl groups. Cycloalkyl groups may include bicycloalkyl and tricycloalkyl groups. The alkyl group is optionally substituted. Substituted alkyl groups include, in particular, alkyl groups substituted with aryl groups, which in turn may be optionally substituted. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, branched butyl, cyclobutyl, n-pentyl, branched pentyl, cyclopentyl, n-hexyl, branched hexyl and cyclohexyl, all of which are optionally substituted. Substituted alkyl groups include perhalogenated or semi-halogenated alkyl groups, such as alkyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms. Substituted alkyl groups include perfluorinated or semi-fluorinated alkyl groups, such as alkyl groups having one or more hydrogens substituted with one or more fluorine atoms. Substituted alkyl groups include alkyl groups substituted with one or more methyl, ethyl, halogen (e.g., fluorine) or trihalomethyl (e.g., trifluoromethyl).

Alkoxy is an alkyl group modified by attachment to oxygen and may be represented by the formula R-O, and may also be referred to as an alkyl ether group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and heptoxy. Alkoxy includes substituted alkoxy groups in which the alkyl portion of the group is substituted as provided herein with respect to the description of alkyl. As used herein, meO-refers to CH ₃ O–。

Alkenyl groups include straight chain alkenyl groups, branched alkenyl groups, and cycloalkenyl groups. Alkenyl includes alkenyl groups having 1, 2 or more double bonds and alkenyl groups in which two or more double bonds are conjugated double bonds. Alkenyl groups include alkenyl groups having 2 to 20 carbon atoms. Alkenyl groups include small alkenyl groups having 2 to 4 carbon atoms. Alkenyl groups include medium length alkenyl groups having 5 to 10 carbon atoms. Alkenyl groups include alkenyl groups having more than 10 carbon atoms, in particular alkenyl groups having from 10 to 20 carbon atoms. Cycloalkenyl includes cycloalkenyl wherein the double bond is in the ring or in the alkenyl group attached to the ring. The term "cycloalkenyl" particularly refers to alkenyl groups having a ring structure, including alkenyl groups having a three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocyclic ring, particularly alkenyl groups having a three-, four-, five-, six-, or seven-membered ring. Carbocycles in cycloalkenyl groups may also bear alkyl groups. Cycloalkenyl groups may include bicycloalkenyl and tricycloalkenyl. Alkenyl groups are optionally substituted. Substituted alkenyl includes in particular alkenyl substituted by alkyl or aryl, which in turn may be optionally substituted. Specific alkenyl groups include vinyl, prop-1-enyl, prop-2-enyl, cycloprop-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl, pent-1-enyl, pent-2-enyl, branched pentenyl, cyclopent-1-enyl, hex-1-enyl, branched hexenyl, cyclohexenyl, all of which are optionally substituted. Substituted alkenyl groups include perhalogenated or semi-halogenated alkenyl groups, for example alkenyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms. Substituted alkenyl groups include perfluorinated or semi-fluorinated alkenyl groups, such as alkenyl groups having one or more hydrogen atoms substituted with one or more fluorine atoms. Substituted alkenyl groups include alkenyl groups substituted with one or more methyl, ethyl, halogen (e.g., fluorine) or trihalomethyl (e.g., trifluoromethyl).

Aryl includes groups having one or more five-, six-or 7-membered aromatic and/or heterocyclic aromatic rings. The term heteroaryl refers specifically to an aryl group having at least one five-, six-or 7-membered heterocyclic aromatic ring. An aryl group may contain one or more fused aromatic and heteroaromatic rings or a combination of one or more aromatic or heteroaromatic rings with one or more non-aromatic rings that may be fused or linked by covalent bonds. The heterocyclic aromatic ring may include one or more N, O or S atoms, etc. in the ring. The heterocyclic aromatic ring may include a heterocyclic aromatic ring having one, two or three N atoms, a heterocyclic aromatic ring having one or two O atoms and a heterocyclic aromatic ring having one or two S atoms, or a combination of one or two or three N, O or S atoms, or the like. Aryl groups are optionally substituted. Substituted aryl includes in particular aryl substituted by alkyl or alkenyl which in turn may be optionally substituted. Specific aryl groups include phenyl, biphenyl, pyrrolidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, and naphthyl, all of which are optionally substituted. Substituted aryl groups include perhalogenated or semi-halogenated aryl groups, such as aryl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms. Substituted aryl groups include perfluorinated or semi-fluorinated aryl groups, such as aryl groups having one or more hydrogens substituted with one or more fluorine atoms. Aryl groups include, but are not limited to, aromatic-or heterocyclic-aromatic-containing groups corresponding to any of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, naphthacene, naphthacenedione, pyridine, quinoline, isoquinoline, indole, isoindole, pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furan, benzofuran, dibenzofuran, carbazole, acridine, acridone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthene, xanthone, flavone, coumarin, azulene, or anthracyclines. As used herein, groups corresponding to the groups listed above expressly include aromatic or heterocyclic aromatic groups, including monovalent, divalent, and multivalent groups, with the aromatic and heterocyclic aromatic groups listed herein being provided in covalently bonded configuration at any suitable point of attachment in the disclosed compounds. In embodiments, aryl groups contain 5 to 30 carbon atoms. In embodiments, the aryl group comprises one aromatic or heteroaromatic six-membered ring and one or more additional five-or six-membered aromatic or heteroaromatic rings. In embodiments, aryl groups contain 5 to 18 carbon atoms in the ring. The aryl group optionally has one or more aromatic or heterocyclic aromatic rings with one or more electron donating groups, electron withdrawing groups, and/or targeting ligands provided as substituents. Substituted aryl groups include aryl groups substituted with one or more methyl, ethyl, halogen (e.g., fluorine) or trihalomethyl (e.g., trifluoromethyl).

Arylalkyl and alkylaryl are alkyl groups substituted with one or more aryl groups, wherein the alkyl groups optionally bear additional substituents and the aryl groups are optionally substituted. Specific alkylaryl groups are phenyl substituted alkyl groups such as benzyl. Alternatively, alkylaryl and arylalkyl groups are described as aryl groups substituted with one or more alkyl groups, wherein the alkyl groups optionally bear additional substituents and the aryl groups are optionally substituted. Specific alkylaryl groups are alkyl substituted phenyl groups, such as methylphenyl. Substituted arylalkyl groups include perhalogenated or semi-halogenated arylalkyl groups, such as arylalkyl groups having one or more alkyl groups and/or arylalkyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms.

With respect to any group described herein that contains one or more substituents, it is to be understood that such groups do not contain any substitution or pattern of substitution that is sterically impractical and/or synthetically infeasible. Furthermore, the disclosed compounds include all stereochemical isomers resulting from the substitution of these compounds. Optional substitution of alkyl includes substitution with one or more alkenyl groups, aryl groups, or both, wherein alkenyl or aryl groups are optionally substituted. Optional substitution of alkyl includes substitution with one or more alkyl groups, aryl groups, or both, wherein alkyl or aryl groups are optionally substituted. Optional substitution of aryl includes substitution of the aromatic ring with one or more alkyl groups, alkenyl groups, or both, wherein the alkyl or alkenyl groups are optionally substituted.

Optional substituents for any alkyl, alkenyl or aryl include substitution with one or more of the following substituents, etc.:

halogen, including fluorine, chlorine, bromine or iodine;

pseudohalides, including-CN;

-COOR, wherein R is hydrogen or alkyl or aryl, or more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

-COR, wherein R is hydrogen or alkyl or aryl, or more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

–CON(R) ₂ wherein each R is independently of the others hydrogen or alkyl or aryl, or more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may optionally form a ring, which may contain one or more bis(s)A bond and may contain one or more additional carbon atoms;

–OCON(R) ₂ wherein each R is independently of the others hydrogen or alkyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may optionally form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

–N(R) ₂ Wherein each R is independently from the others hydrogen or alkyl or acyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl, phenyl or acetyl, all of which are optionally substituted; and wherein R and R may optionally form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

-SR, wherein R is hydrogen or alkyl or aryl, or more specifically wherein R is hydrogen, methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

–SO ₂ r or-SOR, wherein R is alkyl or aryl, or more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

-OCOOR, wherein R is alkyl or aryl;

–SO ₂ N(R) ₂ wherein each R is independently of the others hydrogen, alkyl or aryl, all of which are optionally substituted; and wherein R and R may optionally form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

-OR, wherein R is H, alkyl, aryl OR acyl, all of which may be optionally substituted. In particular embodiments, R may be acyl, yielding-OCOR ", wherein R" is hydrogen or alkyl or aryl, more particularly wherein R "is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted.

Specific substituted alkyl groups include haloalkyl, particularly trihalomethyl, particularly trifluoromethyl. Specific substituted aryl groups include mono-, di-, tri-, tetra-and pentahalo-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa-, and heptahalogen-substituted naphthyl; 3-or 4-halogen substituted phenyl, 3-or 4-alkyl substituted phenyl, 3-or 4-alkoxy substituted phenyl, 3-or 4-RCO substituted phenyl, 5-or 6-halogen substituted naphthyl. More specifically, substituted aryl groups include acetylphenyl, especially 4-acetylphenyl; fluorophenyl, in particular 3-fluorophenyl and 4-fluorophenyl; chlorophenyl, in particular 3-chlorophenyl and 4-chlorophenyl; methylphenyl, in particular 4-methylphenyl; and methoxyphenyl, in particular 4-methoxyphenyl.

The term "electron acceptor" refers to a chemical composition that can accept an electron from another structure or compound. In some cases, the term electron acceptor may be used in a relative sense to identify a compound or subunit thereof as having a stronger affinity for receiving additional electrons than another compound or subunit. In organic photovoltaics, the electron acceptor may be a compound that has the ability to accept electrons from an electron donor. The electron acceptor may be a photoactive compound that generates electron-hole pairs (excitons) upon light absorption of light and may transfer the generated holes to an electron donor.

The term "electron donor" refers to a chemical composition that can donate an electron to another structure or compound. In some cases, the term electron donor may be used in a relative sense to identify a compound or subunit thereof as having a weaker affinity to receive additional electrons than another compound or subunit. In organic photovoltaics, the electron donor may be a compound having the ability to transfer electrons to an electron acceptor. The electron donor may be a photoactive compound that generates electron-hole pairs (excitons) upon light absorption of light and may transfer the generated electrons to an electron acceptor.

"planarity-disrupting moiety" or "disrupting moiety" refers to a moiety or subunit of a compound whose atomic arrangement (e.g., an atomic arrangement of non-hydrogen atoms, such as carbon atoms and/or heteroatoms) is offset from the atomic arrangement (e.g., a planar arrangement of non-hydrogen atoms, such as carbon atoms and/or heteroatoms) of another moiety of the compound. In one embodiment, the compound may include a planar portion in which all or a majority of non-hydrogen atoms (e.g., carbon atoms and/or heteroatoms) and optional hydrogen atoms fall within the plane of the chemical structure of the atoms, and further include a planar failure portion in which the atoms (e.g., non-hydrogen atoms, such as carbon and/or heteroatoms) of the planar failure portion extend out of the plane of or substantially deviate from the plane of the other portion of the compound, such as in a configuration where the atoms are conformationally locked out of the plane of the rest of the compound. In some examples, the planarity disrupting moiety is referred to herein as a Z group. In some cases, when a compound disclosed herein contains multiple planarity disrupting moiety attachment sites (e.g., multiple Z groups), both planarity disrupting moieties may comprise the same substructure; this configuration may be referred to herein as Z and Z forming a ring. In some cases, the planarity disrupting moiety is bonded to a quaternary center that may be a carbon or heteroatom (e.g., si or Ge). In some cases, the quaternary center may be a component of two independent but linked ring structures, also known as spiro compounds. The presence of planarity disrupting moieties in a compound affects volumetric properties such as crystal packing efficiency or density, which can be seen or affected from other molecular properties such as vapor pressure, melting enthalpy, sublimation enthalpy, or yields obtained by sublimation purification. In embodiments, donor portion D comprising one or more planarity disrupting portions may be referred to herein as a nuclear disrupting portion. Similarly, photoactive compounds comprising a donor moiety D comprising one or more planarity disrupting moieties may be referred to herein as core-disrupting photoactive compounds.

"pi-bridging moiety" or "pi-bridging moiety" refers to a moiety or subunit of a compound that provides prolonged conjugation of pi-electrons or optionally p-electrons and is linked between different moieties of the compound by a divalent structure. Prolonged conjugation may occur when the bonds in the compound are in an alternating configuration of single and multiple bonds (e.g., double or triple bonds). In some cases, prolonged conjugation may contribute additional electrons to the aromatic system.

The term "conformationally locked" refers to a configuration wherein the compound orAtoms of a group restrict free rotation or movement of its components in a bonded arrangement. The number of permutations that can be employed by the atoms of the conformationally locked group may be limited. As an example, a screw group may be conformationally locked in that the atoms of the two ring structures that make up the group are not free to rotate relative to each other; this configuration is in contrast to groups in which subunit free rotation can occur. Examples of groups that are not conformationally locked may include some alkyl groups, such as methyl, ethyl, propyl or butyl, where methyl (-CH) ₃ ) Ethyl (CH) ₂ CH ₃ ) Etc. may be rotated. In some cases, the space may restrict rotation of certain groups. In some cases, a conformationally locked group whose configuration is out of the plane of another component of the compound may not be able to be positioned in the plane due to the bonding arrangement of atoms in the conformationally locked group.

As used herein, the terms visible light transparency, and the like refer to the optical properties of a material that exhibit a total, average, or maximum absorbance in the visible band of from 0% to 70%, such as less than or about 70%, less than or about 65%, less than or about 60%, less than or about 55%, less than or about 50%, less than or about 45%, less than or about 40%, less than or about 35%, less than or about 30%, less than or about 25%, or less than or about 20%. In other words, the visible light transparent material may transmit 30% to 100% of incident visible light, such as greater than or about 80% of incident visible light, greater than or about 75% of incident visible light, greater than or about 70% of incident visible light, greater than or about 65% of incident visible light, greater than or about 60% of incident visible light, greater than or about 55% of incident visible light, greater than or about 50% of incident visible light, greater than or about 45% of incident visible light, greater than or about 40% of incident visible light, greater than or about 35% of incident visible light, or greater than or about 30% of incident visible light. Visible light transparent materials are generally considered to be at least partially transparent (e.g., not completely opaque) when viewed by a person. Alternatively, the visible light transparent material may be colorless when viewed by a person (e.g., not exhibit strong visible light absorbing characteristics that would provide a particular color appearance).

As used herein, the term "visible" refers to a band of electromagnetic radiation to which the human eye is sensitive. For example, visible light may refer to light having a wavelength between about 450nm and about 650 nm.

The term "near infrared" or "NIR" refers to a band of electromagnetic radiation that has a wavelength longer than the wavelength to which the human eye is sensitive. For example, near infrared light may refer to light having a wavelength greater than 650nm, such as between about 650nm and about 1400nm or between about 650nm and 2000 nm.

The term "ultraviolet" or "UV" refers to a band of electromagnetic radiation having a wavelength shorter than the wavelength to which the human eye is sensitive. For example, ultraviolet light may refer to light having a wavelength less than 450nm, such as between about 200nm and about 450nm or between about 280nm and 450 nm.

Although the specific applications described herein are for use as photoactive compounds, such as electron acceptor compounds or electron donor compounds, in organic photovoltaic devices, the disclosed compounds may be used in any application. In some embodiments, the disclosed compounds are paired with a corresponding photoactive material (e.g., an electron donor material or an electron acceptor material) to form a heterojunction structure comprising an electron donor compound and a corresponding electron acceptor material or comprising an electron acceptor compound and a corresponding electron donor material, as described further below, for generating and separating electron-hole pairs for converting electromagnetic radiation (e.g., ultraviolet light, visible light, and/or near-infrared light) into useful electrical energy (e.g., voltage/current). In particular embodiments, the photovoltaic device incorporating one or more of the disclosed photoactive compounds is a visible light transparent photovoltaic device. In other embodiments, the photovoltaic device incorporating one or more of the disclosed photoactive compounds is a partially transparent photovoltaic device, a colored partially transparent photovoltaic device, or an opaque photovoltaic device,

Fig. 3A is a simplified schematic diagram illustrating a photovoltaic device according to some embodiments. As shown in fig. 3A, the photovoltaic device 300 includes a plurality of layers and elements discussed more fully below. As discussed with respect to fig. 4, the photovoltaic device 300 may be visible light transparent, which indicates that the photovoltaic device absorbs light energy at wavelengths outside the visible wavelength band, e.g., 450nm to 650nm, while substantially transmitting visible light within the visible wavelength band. As shown in fig. 3A, UV and/or NIR light is absorbed in the layers and elements of the photovoltaic device, while visible light is transmitted through the device, although in some cases, such as in partially transparent photovoltaic devices or opaque photovoltaic devices, visible light may be absorbed, such as through the photoactive layer.

Substrate 305 may be glass or other visible light transparent material that provides sufficient mechanical support for the other layers and structures shown, with substrate 305 supporting optical layers 310 and 312. These optical layers may provide a variety of optical properties including anti-reflection (AR) properties, wavelength selective reflection or distributed bragg reflection properties, refractive index matching properties, encapsulation, etc. The optical layer may advantageously be visible light transparent. Additional optical layers 314 may be used, for example, as AR coatings, index matching layers, passive infrared or ultraviolet absorbing layers, and the like. Alternatively, the optical layer may be transparent to ultraviolet and/or near infrared light, or at least transparent to sub-wavelengths in the ultraviolet and/or near infrared bands. Depending on the configuration, the additional optical layer 314 may also be, for example, a passive visible light absorbing layer or a neutral filter. Example substrate materials include various glasses and rigid or flexible polymers. A multi-layer substrate may also be used. The substrate may have any suitable thickness to provide the mechanical support required for other layers and structures, for example a thickness of 1mm to 20 mm. In some cases, the substrate may be or include an adhesive film to allow application of the photovoltaic device 300 to another structure, such as a window pane, display device, or the like.

It should be understood that while some of the devices described herein exhibit visible light transparency, photovoltaic devices that are not completely visible light transparent are also disclosed herein, as some of the photoactive compounds described herein may exhibit visible light absorption. In the case of a visible light transparent photovoltaic device exhibiting visible light transparency as a whole (e.g., a transparency greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, or up to or near 100% in the range of 450-650 nm), the use of certain materials alone may exhibit absorption in a portion of the visible spectrum. Optionally, each individual material or layer in the visible light transparent photovoltaic device has a high transparency in the visible range, for example greater than 30% (e.g., between 30% and 100%). It should be appreciated that transmission or absorption may be expressed in percent and may depend on the absorption properties of the material, the thickness or path length through the absorbing material, and the concentration of the absorbing material, such that when the path length through the absorbing material is short and/or the absorbing material is present in low concentrations, a material having absorption in the visible spectrum may still exhibit low absorption or high transmission.

As described herein and below, the various photoactive materials in the various photoactive layers advantageously can exhibit minimal absorption (e.g., less than 20%, less than 30%, less than 40%, less than 50%, less than 60%, or less than 70%) in the visible region, while exhibiting high absorption (e.g., greater than 50%, greater than 60%, greater than 70%, or greater than 80%) in the near infrared and/or ultraviolet regions. For some applications, the absorption in the visible region may be as high as 70%. Various configurations of other materials, such as substrates, optical layers, and buffer layers, may be used to allow these materials to provide overall visible light transparency even though these materials may exhibit some amount of visible light absorption. For example, a metal thin film, such as a metal exhibiting visible light absorption, such as Ag or Cu, may be contained in the transparent electrode; however, when provided in a thin film configuration, the overall transparency of the film may be high. Similarly, the material contained in the optical layer or the buffer layer may exhibit absorption in the visible light range, but may be provided at a concentration or thickness low in the total amount of visible light absorption, thereby providing visible light transparency.

The photovoltaic device 300 also includes a set of transparent electrodes 320 and 322, with a photoactive layer 340 located between the electrodes 320 and 322. These electrodes, which may be fabricated using ITO, metal films, or other suitable visible light transparent materials, provide electrical connection to one or more of the layers shown. For example, thin films of copper, silver, or other metals may be suitable for use as visible light transparent electrodes, even though these metals may absorb light in the visible light band. However, when provided as a film, for example, a film having a thickness of 1nm to 200nm (about 5nm, about 10nm, about 15nm, about 20nm, about 25nm, about 30nm, about 35nm, about 40nm, about 45nm, about 50nm, about 55nm, about 60nm, about 65nm, about 70nm, about 75nm, about 80nm, about 85nm, about 90nm, about 95nm, about 100nm, about 105nm, about 110nm, about 115nm, about 120nm, about 125nm, about 130nm, about 135nm, about 140nm, about 145nm, about 150nm, about 155nm, about 160nm, about 165nm, about 170nm, about 175nm, about 180nm, about 185nm, about 190nm, or about 195 nm), the overall transmittance of the film in the visible light band may remain relatively high, for example, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80% or greater than 90%. Advantageously, when used as a transparent electrode, the metallic film may have a lower absorption in the ultraviolet band than other semiconductor materials (e.g., ITO) that may be used as transparent electrodes, because some semiconductor transparent conductive oxides exhibit a band gap that occurs in the ultraviolet band and thus is highly absorptive or opaque to ultraviolet light. However, in some cases, transparent electrodes that absorb ultraviolet light may be used, such as shielding at least a portion of the ultraviolet light from underlying components, as ultraviolet light may degrade certain materials.

The transparent electrode may be produced using a variety of deposition techniques, including vacuum deposition techniques such as atomic layer deposition, chemical vapor deposition, physical vapor deposition, vacuum thermal evaporation, sputter deposition, epitaxy, and the like. Solution-based deposition techniques, such as spin-coating, may also be used in some cases. In addition, various components such as transparent electrodes may be patterned using techniques known in the art of micromachining, including photolithography, lift-off, etching, and the like.

Buffer layers 330 and 332 and photoactive layer 340 are used to achieve the electrical and optical properties of the photovoltaic device. These layers may be single material layers or may include multiple sub-layers suitable for a particular application. Thus, the term "layer" is not intended to mean a single layer of a single material, but may include multiple sub-layers of the same or different materials. In some cases, the layers may partially or completely overlap. In some embodiments, buffer layer 330, photoactive layer 340, and buffer layer 332 are repeated in a stacked configuration to provide a tandem device configuration, for example, including a plurality of heterojunctions. In some examples, the photoactive layer includes an electron donor material and an electron acceptor material, also referred to as a donor and acceptor. In some cases, these donors and acceptors may be visible light transparent, but absorb outside the visible light band to provide photoactive properties of the device. In the case of partially transparent and opaque photovoltaic devices, the donor and/or acceptor may absorb in the visible region.

Useful buffer layers include those that function as electron transport layers, electron blocking layers, hole transport layers, hole blocking layers, exciton blocking layers, optical spacers, physical buffer layers, charge recombination layers, or charge generation layers. The cushioning layer may exhibit any suitable thickness to provide the desired cushioning effect and may optionally be present or absent. Useful buffer layers, if present, may be 1nm to 1 μm thick. A variety of materials may be used as the buffer layer, including fullerenic materials, carbon nanotube materials, graphene materials, metal oxides (e.g., molybdenum oxide, titanium oxide, zinc oxide, etc.), polymers (e.g., poly (3, 4-ethylenedioxythiophene), polystyrene sulfonic acid, polyaniline, etc.), copolymers, polymer mixtures, and small molecules such as bathocuproine. The buffer layer may be applied using a deposition process (e.g., vacuum thermal evaporation) or a solution processing method (e.g., spin coating).

Fig. 3B depicts an overview of various exemplary single connection configurations for photoactive layer 340. Photoactive layer 340 can optionally correspond to a hybrid donor/acceptor (bulk heterojunction) configuration, a planar donor/acceptor configuration, a planar and hybrid donor/acceptor configuration, or a gradient donor/acceptor configuration. Various materials may be used as the photoactive layer 340, such as a visible light transparent material that absorbs in the ultraviolet or near infrared band and absorbs only minimally, if at all, in the visible band. In this way, the photoactive material may be used to generate electron-hole pairs for powering external circuitry through ultraviolet and/or near infrared absorption, leaving visible light relatively undisturbed to provide visible light transparency. However, in other cases, the photoactive layer 340 can include a material that absorbs in the visible light region. As shown, photoactive layer 340 can include a planar heterojunction that includes separate donor and acceptor layers. Alternatively, photoactive layer 340 can comprise a planar hybrid heterojunction structure comprising separate acceptor and donor layers and a hybrid donor-acceptor layer. Alternatively, photoactive layer 340 can comprise a mixed heterojunction structure comprising a fully mixed acceptor-donor layer or comprising a mixed donor-acceptor layer having various relative concentration gradients.

Photoactive layer 340 can have any suitable thickness, and can have any suitable concentration or composition of photoactive material to provide a desired level of transparency and ultraviolet/near infrared absorption characteristics. Example thicknesses of the photoactive layer may range from about 1nm to about 1 μm, from about 1nm to about 300nm, or from about 1nm to about 100 nm. In some cases, photoactive layer 340 can be composed of a single sub-layer, or a mixture of layers, to provide suitable photovoltaic power generation features, as shown in fig. 3B. Various configurations shown in fig. 3B may be used and depend on the particular donor and acceptor materials used to provide advantageous photovoltaic power generation. For example, some donor and acceptor combinations may benefit from a particular configuration, while other donor and acceptor combinations may benefit from other particular configurations. The donor material and the acceptor material may be provided in any ratio or concentration to provide suitable photovoltaic power generation characteristics. For mixed layers, the relative concentrations of donor and acceptor are optionally at about 20:1 and about 1: 20. Optionally, the relative concentration of donor to acceptor is optionally at about 5:1 and about 1: 5. Alternatively, the donor and acceptor were combined at 1:1 is present.

It should be appreciated that in various embodiments, photovoltaic device 300 includes transparent electrode 320, photoactive layer 340, and transparent electrode 322, and may optionally include or exclude any one or more of substrate 305, optical layers 310, 312, and 314, and/or buffer layers 330 and 332.

As described more fully herein, the disclosed embodiments may use photoactive compounds for one or more of the buffer layer, the optical layer, and/or the photoactive layer. These compounds may include suitable functionalized forms for modifying the electrical and/or optical properties of the core structure. As one example, the disclosed compounds may include functional groups that reduce absorption properties in the visible band between 450nm and 650nm and increase absorption properties in the NIR band at wavelengths greater than 650 nm.

As an example, the disclosed photoactive compounds can be used as electron acceptor materials or electron donor materials, and can be paired with suitable corresponding materials having opposite properties, such as corresponding electron donor materials or corresponding electron acceptor materials, in order to provide a useful heterojunction-based photoactive layer in a photovoltaic device. Example electron donor photoactive materials or electron acceptor photoactive materials may be visible light transparent. In the case of partially transparent, or opaque, photovoltaic devices, the photoactive material may absorb light in the visible region.

In embodiments, the chemical structure of the photoactive compound may be functionalized with one or more directing groups, such as electron donating groups, electron withdrawing groups, or substitution of or around the core metal atom or group, in order to provide the material with desired electrical characteristics. For example, in some embodiments, the photoactive compound is functionalized with amine groups, phenol groups, alkyl groups, phenyl groups, or other electron donating groups to enhance the ability of the material to act as an electron donor in a photovoltaic device. As another example, photoactive compounds may be functionalized with cyano, halogen, sulfonyl, or other electron withdrawing groups to enhance the ability of the material to act as an electron acceptor in a photovoltaic device.

In embodiments, the photoactive compound is functionalized to provide desired optical characteristics. For example, the photoactive compound may be functionalized with a prolonged conjugation to red shift the absorption spectrum of the material. It is understood that conjugation may refer to the delocalization of pi electrons in a molecule, which may be characterized by alternating single and multiple bonds in the chemical structure of the molecule, and/or the presence of aromatic structures. For example, functionalization to extend electron conjugation may include fusing one or more aromatic groups to the molecular structure of the material. Other functionalities that may provide extended conjugation include olefin functionalization (e.g., via vinyl), aromatic or heteroaromatic functionalization, carbonyl functionalization (e.g., via acyl), sulfonyl functionalization, nitro functionalization, cyano functionalization, and the like. It should be appreciated that various molecular functionalities can affect the optical and electrical properties of the photoactive compounds.

It should be appreciated that device functionality may be affected by the morphology of the active layer in the solid state. The separation of the electron donor and acceptor into discrete domains, whose size is proportional to the exciton diffusion length and large interface area, is advantageous for achieving high device efficiency. Advantageously, the molecular framework of the photoactive material can be tuned to control the morphology of the material. For example, the introduction of functional groups as described herein can have a tremendous impact on the morphology of solid state materials, regardless of whether such modifications affect the energetic or electronic properties of the materials. This morphological change can be observed in pure materials, as well as when a particular material is mixed with the corresponding donor or acceptor. Useful functionalities to control morphology include, but are not limited to, addition of alkyl chains, conjugated linkers, fluorinated alkanes, bulky groups (e.g., t-butyl, phenyl, naphthyl, or cyclohexyl), and more complex coupling procedures designed to force part of the structure out of the molecular plane to inhibit excessive crystallization.

In embodiments, other molecular structural features may provide desirable electrical and optical properties in the photoactive compound. For example, photoactive compounds may exhibit a molecular moiety that may be characterized as electron donating, while other portions of the molecule may be characterized as electron accepting. Without wishing to be bound by any theory, a molecule comprising alternating electron donating and electron accepting moieties may cause the absorption characteristics of the molecule to red shift compared to a similar molecule lacking alternating electron donating and electron accepting moieties. For example, alternating electron donating and electron accepting moieties can reduce or otherwise result in a lower energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Organic donor and/or acceptor groups may be used as R-group substituents in the visible light transparent photoactive compounds described herein, for example, on any aryl (aryl), aromatic (aromatic), heteroaryl, heteroaromatic, alkyl, or alkenyl group. Exemplary acceptor and donor groups are described in more detail below.

In embodiments, the photoactive compound may exhibit a symmetrical structure, such as a structure having two or more points of symmetry. Symmetrical structures may include structures in which a core group is functionalized with the same group on opposite sides, or in which two identical core groups are fused or otherwise bonded to each other. In other embodiments, the photoactive compound may exhibit an asymmetric structure, such as a structure having fewer than two points of symmetry. Asymmetric structures may include structures in which a core group is functionalized with different groups on opposite sides, or in which two different core groups are fused or otherwise bonded to each other.

When the materials described herein are incorporated into a photovoltaic device as photoactive layers, for example, as electron acceptors or electron donors, the layer thickness can be controlled to alter the device output, absorption, or transmittance. For example, increasing the thickness of the donor or acceptor layer may increase the light absorption in the layer. In some cases, increasing the concentration of donor/acceptor material in a donor or acceptor layer can similarly increase light absorption in that layer. However, in some embodiments, the concentration of the donor/acceptor material may not be adjustable, for example, when the active material layer comprises a pure or substantially pure donor/acceptor material layer or a pure or substantially pure donor/acceptor material mixture. Alternatively, the donor/acceptor material may be provided in a solvent or suspended in a carrier (e.g., buffer layer material), in which case the concentration of the donor/acceptor material may be adjusted. In some examples, the donor layer concentration is selected to maximize the current generated. In some examples, the concentration of the acceptor layer is selected to maximize the current generated.

However, as the "travel distance" of the charge carriers increases, the charge collection efficiency decreases with increasing donor or acceptor thickness. Thus, as layer thickness increases, there may be a tradeoff between increased absorption and reduced charge collection efficiency. Thus, it may be advantageous to select materials as described herein that have a high absorption coefficient and/or concentration to allow for increased light absorption per unit thickness. In some embodiments, the donor layer thickness is selected to maximize the current generated. In some embodiments, the thickness of the receptor layer is selected to maximize the current generated.

In addition to the thickness of the individual photoactive layers formed from the materials described herein, the thickness and composition of other layers in the transparent photovoltaic device may also be selected to enhance absorption within the photoactive layers. The other layers (buffer layers, electrodes, etc.) are typically chosen according to their optical properties (refractive index and extinction coefficient) in the context of the thin-film device stack and the resulting optical cavity. For example, the near infrared absorbing photoactive layer may be located at the peak of the optical field at near infrared wavelengths where it absorbs to maximize the absorption and resulting current produced by the device. This may be achieved by using the second photoactive layer and/or the optical layer as a spacer to space the photoactive layer from the electrode by an appropriate distance. Similar schemes can be used for photoactive layers that absorb ultraviolet or visible light. In many cases, the peak of the longer wavelength light field will be located farther from the more reflective of the two transparent electrodes than the peak of the shorter wavelength light field. Thus, when separate donor and acceptor photoactive layers are used, the donor and acceptor can be selected to place more red absorbing (longer wavelength) material farther from the more reflective electrode, and more blue absorbing (shorter wavelength) material closer to the more reflective electrode.

In some embodiments, an optical layer may be included to increase the optical field intensity at the wavelength of donor absorption in the donor layer to increase light absorption and thereby increase the current generated by the donor layer. In some embodiments, an optical layer may be included to increase the intensity of the optical field at the wavelength of absorption of the receptor in the receptor layer to increase light absorption and thereby increase the current generated by the receptor layer. In some examples, the optical layer may be used to increase the transparency of the stack by reducing visible light absorption or visible light reflection. In addition, the electrode material and thickness may be selected to enhance absorption outside the visible range within the photoactive layer while preferentially transmitting light in the visible range.

Alternatively, enhanced spectral coverage of the photovoltaic device is achieved by using a multi-cell tandem photovoltaic device stack, referred to as a tandem cell, which may be included in multiple stacked instances of buffer layer 330, photoactive layer 340, and buffer layer 332, as described with reference to fig. 3A. Such structures include more than one photoactive layer, typically separated by a combination of, for example, buffer layers and/or thin layers of metal. In this configuration, the current generated in each sub-cell flows in series to the opposing electrode, and thus, for example, the net current in the cell is limited by the minimum current generated by the particular sub-cell. The open circuit Voltage (VOC) is equal to the sum of the VOCs of the subcells. By combining sub-cells fabricated using different donor-acceptor pairs that absorb in different regions of the solar spectrum, a significant increase in efficiency relative to single junction cells can be achieved.

Additional description regarding materials used in one or more buffer layers and photoactive layers (including donor layers and/or acceptor layers) is provided below.

Fig. 4 is a simplified graph illustrating solar spectrum, human eye sensitivity, and absorption as a function of wavelength for an exemplary visible light transparent photovoltaic device. As shown in fig. 4, an example of a visible light transparent photovoltaic device may utilize a photovoltaic structure having low absorption in the visible light band between about 450nm and about 650nm but absorption in the UV and NIR bands (e.g., outside the visible light band) to achieve visible light transparent photovoltaic operation. For example, the ultraviolet band or region may be described as a wavelength of light between about 200nm and 450 nm. It should be appreciated that useful solar radiation at ground level may have a limited amount of ultraviolet less than about 280nm, and thus, in some embodiments, the ultraviolet band or region may be described as a wavelength of light between about 280nm and 450 nm. For example, the near infrared band or near infrared region may be described as a wavelength of light between about 650nm and 1400 nm. The various compositions described herein may exhibit absorption, including NIR peaks having an absorption intensity in the visible region that is less than the maximum absorption intensity in the NIR region.

Fig. 5 provides an overview of an energy level diagram for operating an exemplary organic photovoltaic device, such as a visible light transparent photovoltaic device 300. For example, in such photovoltaic devices, various photoactive materials may exhibit electron donor or electron acceptor characteristics, depending on their properties and the type of material used for the buffer layer, corresponding material, electrode, etc. As shown in fig. 5, each of the donor material and the acceptor material has a Highest Occupied Molecular Orbital (HOMO) and a Lowest Unoccupied Molecular Orbital (LUMO). The transition of electrons from HOMO to LUMO can be achieved by absorption of photons. The energy between the HOMO and LUMO of a material (HOMO-LUMO energy gap) approximately represents the energy of the optical bandgap of the material. For electron donor and electron acceptor materials that may be used in the transparent photovoltaic devices provided herein, the HOMO-LUMO energy gap of the electron donor and electron acceptor materials preferably falls outside the photon energy in the visible range. For example, the HOMO-LUMO energy gap may be located in the ultraviolet region or the near infrared region, depending on the photoactive material. In some cases, the HOMO-LUMO energy gap may overlap with or with the visible and ultraviolet regions in the visible or region, such as for partially transparent or opaque photovoltaic devices. It should be understood that HOMO corresponds to the valence band in a conventional conductor or semiconductor, while LUMO corresponds to the conduction band in a conventional conductor or semiconductor.

The narrow absorption spectrum of many organic molecules (e.g., organic semiconductors) makes it difficult to absorb the entire absorption spectrum using a single molecular species. Thus, electron donor and acceptor molecules are typically paired to provide complementary absorption spectra and increase spectral coverage of light absorption. Furthermore, the donor and acceptor molecules are chosen such that their energy levels (HOMO and LUMO) are in a favorable position with respect to each other. The difference in LUMO levels of the donor and acceptor provides a driving force for dissociation of electron-hole pairs (excitons) generated at the donor, while the difference in HOMO levels of the donor and acceptor provides a driving force for dissociation of electron-hole pairs (excitons) generated at the acceptor. In some embodiments, it may be useful for the acceptor to have a high electron mobility to efficiently transport electrons to the adjacent buffer layer. In some embodiments, it may be useful for the donor to have a high hole mobility to efficiently transport holes to the buffer layer. Further, in some examples, it may be useful to increase the difference between the LUMO energy level of the acceptor and the HOMO energy level of the donor to increase the open circuit Voltage (VOC), as VOCs have been demonstrated to be proportional to the difference between the LUMO of the acceptor and the HOMO of the donor. Such donor-acceptor pairing within the photoactive layer may be achieved by appropriately pairing one of the materials described herein with a complementary material, which may be a different photoactive compound or a completely independent material system as described herein.

The buffer layer adjacent to the donor, commonly referred to as the anode buffer layer or hole transport layer, is selected such that the HOMO level or valence band of the buffer layer (in the case of inorganic materials) is aligned with the HOMO level of the donor in the energy landscape to transport holes from the donor to the anode (transparent electrode). In some embodiments, it may be useful for the buffer layer to have a high hole mobility. The buffer layer adjacent to the acceptor, commonly referred to as the cathode buffer layer or electron transport layer, is selected such that the LUMO level or conduction band (in the case of inorganic materials) of the buffer layer is aligned with the LUMO level of the acceptor in the energy landscape to transport electrons from the acceptor to the cathode (transparent electrode). In some embodiments, it may be useful for the buffer layer to have a high electron mobility.

Exemplary diagrams illustrating absorption bands for different electron donor and electron acceptor configurations useful for visible light transparent photovoltaic devices are provided in fig. 6A, 6B, 6C, and 6D. In fig. 6A, the donor material exhibits absorption in NIR and the acceptor material exhibits absorption in UV. Fig. 6B depicts the opposite configuration, where the donor material exhibits absorption in UV and the acceptor material exhibits absorption in NIR.

Fig. 6C depicts an additional configuration in which both donor and acceptor materials exhibit absorption in the NIR. As shown, the solar spectrum exhibits a large amount of useful radiation in the NIR and only a relatively small amount of useful radiation in the uv, so that the configuration shown in fig. 6C can be used to capture a large amount of energy from the solar spectrum. It should be appreciated that other examples are contemplated in which both donor and acceptor materials exhibit absorption in the NIR, such as shown in fig. 6D, where the acceptor is blue-shifted relative to the donor, as opposed to the configuration shown in fig. 6C, where the donor is blue-shifted relative to the acceptor.

The present disclosure also provides methods of manufacturing photovoltaic devices, such as photovoltaic device 300. For example, fig. 7 provides an overview of a method 700 for manufacturing a photovoltaic device according to some embodiments. The method 700 begins at block 705, where a transparent substrate is provided. It should be appreciated that useful transparent substrates include substrates that are transparent to visible light, such as glass, plastic, quartz, and the like. Flexible and rigid substrates may be used for various examples. Optionally, the transparent substrate has one or more optical layers preformed on the top and/or bottom surfaces.

At block 710, one or more optical layers are optionally formed on or over a transparent substrate, such as on a top surface and/or a bottom surface of the transparent substrate. Optionally, one or more optical layers are formed on other materials, such as interlayers or materials, such as transparent conductors. Optionally, one or more optical layers are positioned adjacent to and/or in contact with the visible light transparent substrate. It should be appreciated that the formation of the optical layer is optional and that some embodiments may not include an optical layer adjacent to and/or in contact with the transparent substrate. The optical layer may be formed using a variety of methods including, but not limited to, one or more chemical deposition methods such as electroplating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, or one or more physical deposition methods such as vacuum thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition. It should be understood that useful optical layers include visible light transparent optical layers. Useful optical layers include optical layers that provide one or more optical properties, including, for example, anti-reflection properties, wavelength selective reflection or distributed Bragg reflection properties, index matching properties, encapsulation, and the like. Useful optical layers may optionally include optical layers that are transparent to ultraviolet and/or near infrared light. However, depending on the configuration, some optical layers may optionally provide passive infrared and/or ultraviolet absorption. Alternatively, the optical layer may comprise a visible light transparent photoactive compound as described herein.

At block 715, a transparent electrode is formed. As described above, the transparent electrode may correspond to an indium tin oxide thin film or other transparent conductive film, such as a metal thin film (e.g., ag, cu, etc.), a multi-layer stack including a metal thin film (e.g., ag, cu, etc.), and a dielectric material or a conductive organic material (e.g., a conductive polymer, etc.). It should be understood that transparent electrodes include electrodes that are transparent to visible light. The transparent electrode may be formed using one or more deposition processes, including vacuum deposition techniques such as atomic layer deposition, chemical vapor deposition, physical vapor deposition, vacuum thermal evaporation, sputter deposition, epitaxy, and the like. Solution-based deposition techniques, such as spin-coating, may also be used in some cases. In addition, the transparent electrode may be patterned by a micromachining technique such as photolithography, lift-off, etching, and the like.

At block 720, one or more buffer layers are optionally formed, for example, on the transparent electrode. The buffer layer may be formed using a variety of methods including, but not limited to, one or more chemical deposition methods such as electroplating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, or one or more physical deposition methods such as vacuum thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition. It should be appreciated that useful buffer layers include visible light transparent buffer layers. Useful buffer layers include buffer layers that function as electron transport layers, electron blocking layers, hole transport layers, hole blocking layers, optical spacers, physical buffer layers, charge recombination layers, or charge generation layers. In some cases, the disclosed visible light transparent photoactive compounds can be used as buffer layer materials. For example, the buffer layer may optionally include a visible light transparent photoactive compound as described herein.

At block 725, one or more photoactive layers are optionally formed, such as on a buffer layer or on a transparent electrode. As described above, the photoactive layer may comprise an electron acceptor layer and an electron donor layer or a co-deposited layer of an electron donor and acceptor. Useful photoactive layers include photoactive layers comprising photoactive compounds described herein. The photoactive layer may be formed using a variety of methods including, but not limited to, one or more chemical deposition methods such as electroplating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, or one or more physical deposition methods such as vacuum thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.

In some embodiments, the photoactive compound for the photoactive layer may be deposited using vacuum deposition techniques, such as vacuum thermal evaporation. Vacuum deposition can be performed inIn a vacuum chamber, e.g. at about 10 ^–5 Torr and about 10 ^–8 Under pressure between Torr. In one embodiment, the vacuum deposition may be at about 10 ^–7 Occurs under the pressure of Torr. As described above, various deposition techniques may be applied. In some embodiments, thermal evaporation is used. Thermal evaporation may include heating a source of material to be deposited (e.g., a visible light transparent photoactive compound) to a temperature between 150 ℃ and 500 ℃. The temperature of the material source may be selected to achieve a film growth rate between about 0.01nm/s and about 1 nm/s. For example, a film growth rate of 0.1nm/s may be used. These growth rates can be used to produce thin films between about 1nm and 500nm in thickness over the course of minutes to hours. It should be appreciated that various properties of the deposited material (e.g., molecular weight, volatility, thermal stability) can determine or affect the source temperature or maximum usable source temperature. For example, the thermal decomposition temperature of the deposited material may limit the maximum temperature of the source. As another example, a highly volatile deposition material may require a lower source temperature to achieve a target deposition rate than a less volatile material that may require a higher source temperature to achieve the target deposition rate. When the deposited material evaporates from the source, it can be deposited on a surface (e.g., substrate, optical layer, transparent electrode, buffer layer, etc.) at a lower temperature. For example, the surface may have a temperature of about 10 ℃ to about 100 ℃. In some cases, the surface temperature may be actively controlled. In some cases, the surface temperature may not be actively controlled.

At block 730, one or more buffer layers are optionally formed, for example, on the photoactive layer. The buffer layers formed at block 730 may be formed similar to those formed at block 720. It should be appreciated that blocks 720, 725, and 730 may be repeated one or more times, for example, to form a multi-layer material stack including a photoactive layer and optionally various buffer layers.

At block 735, a second transparent electrode is formed, for example, on the buffer layer or on the photoactive layer. The second transparent electrode may be formed using techniques suitable for forming the first transparent electrode at block 715.

At block 740, one or more additional optical layers are optionally formed, such as on the transparent electrode.

It should be appreciated that the specific steps shown in fig. 7 provide a specific method of manufacturing a photovoltaic device according to various embodiments. Other sequences of steps may be performed according to alternative embodiments. For example, alternative embodiments may perform the steps outlined above in a different order. Further, each step shown in fig. 7 may include a plurality of sub-steps, which may be performed in various orders suitable for each step. Furthermore, additional steps may be added or deleted depending on the particular application. It should be understood that many variations, modifications and alternatives may be used.

Method 700 may optionally be extended to correspond to a method for generating electrical energy. For example, a method for generating electrical energy may include providing a photovoltaic device, such as by manufacturing the photovoltaic device according to method 700. The method for generating electrical energy may further comprise exposing the photovoltaic device to visible, ultraviolet and/or near infrared light to drive the formation and separation of electron-hole pairs, as described above with reference to fig. 5, for example, for generating electrical energy. The photovoltaic device can include the photoactive compounds described herein as photoactive materials, buffer materials, and/or optical layers.

Turning now to further details regarding photoactive compounds, in some embodiments, photoactive compounds described herein comprise a molecular composition having the structure a-D-A, A-pi-D-A, A-pi-D-pi-A, A-D or a-pi-D, wherein each "a" moiety is an electron acceptor moiety, "D" moiety is an electron donor moiety, and "pi" moiety is a pi-bridging moiety. Advantageously, the photoactive compound may have a molecular weight that makes it suitable for physical vapor deposition techniques, for example a molecular weight of 200amu to 1200 amu, for example 200amu to 900amu, 200amu to 950amu, 200amu to 1000amu, 200amu to 1050amu, 200amu to 1100amu. Photoactive compounds at 0.2Torr to 10 ^–7 The pressure of Torr may exhibit a thermal decomposition temperature of 150℃to 500℃or greater than 500℃and/or a sublimation temperature of 150℃to 450 ℃. These features may help or impart stability, making the photoactive compounds suitable for usePhysical vapor deposition process.

The photoactive compound may exhibit optical properties as described above, for example, wherein the photoactive compound exhibits absorption in the ultraviolet, visible, and/or infrared regions. In some cases, the compounds exhibit a band gap of 0.5eV to 4.0eV. For visible light transparent photoactive compounds, the band gap may be 0.5eV to 1.9eV or 2.7eV to 4.0eV.

Each of the different A, pi and D moieties in the photoactive compound affects the absorption spectrum and volatility. Without limitation, each "a" moiety in the photoactive compound may be independently selected from:

wherein each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, wherein each Y ¹ Independently C (CN) ₂ O, S or cyanoimines (N-CN), wherein each Y ² Independently CH or N or Y ² In the absence, part A is linked to part D or pi by a double bond, where each X ¹ O, S, se, or C1-C8 alkylated N (e.g., NR) ^N Or NR (NR) ^O For example, where R ^N Is C1-C8 alkyl), and wherein each R ³ Is CN or C (CN) ₂ And wherein R is ^O Is a branched or linear C1-C8 alkyl group, the branched or linear C1-C8 alkyl group having, for example, a molecular weight of from 15amu to 100 amu. In some examples, Y ² Absence in part A indicates that part APart comprises->In which case the double bond is attached to the pi moiety, e.g. when pi packetsContainingWhen (1).

In some cases, it may be desirable for at least one Y in the photoactive compound ¹ Is O or S, not C (CN) ₂ . Although O is used instead of C (CN) ₂ As Y in section A ¹ The molecular weight may be reduced by about 48amu, but the resulting photoactive compound may exhibit a greater increase in vapor pressure and volatility than would be expected for only such a change in molecular weight. Similarly, S is used instead of C (CN) ₂ As Y in section A ¹ The molecular weight can be reduced by about 32amu, but the resulting photoactive compound can exhibit a greater increase in vapor pressure and volatility than would be expected for only such a change in molecular weight.

In some cases, it may be desirable for at least one Y in the photoactive compound ² Is N, not CH or a double bond. Such a section a may be referred to as havingA structure wherein a' is an imine-linked electron acceptor moiety, which may be or comprise a heterocycle that may be substituted or unsubstituted. In some embodiments, a may be an imine linked indandione, an imine linked dicyandiamide indanone, an imine linked bis (dicyandiamide) indane, or an imine linked dicyanoethylene. Using N instead of CH or double bond linkages as Y ² An increase in molecular weight of about 1amu can result, but other properties can also be altered. For example, N is used as Y instead of CH or double bond linkage ² Can result in a change in the optical properties of the photoactive compound. As an example, a red shift of the maximum absorption, e.g. 50 to 100nm, can be achieved by using an imine linkage between the a-part and the D-part or pi-part. In another embodiment, the reduction in band gap may be achieved by using an imine linkage between the a moiety and the D moiety or pi moiety, for example by about 0.25eV to 0.75eV.

Without limitation, each "pi" moiety in the photoactive compound may be independently selected from:

wherein each X ¹ Independently O, S, se or C1-C8 alkylated N (e.g., NR ^N Or NR (NR) ^O For example wherein R is C1 to C8 alkyl), each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, each W is independently H, F, or branched or straight-chain C1-C8 alkyl or branched or straight-chain C1-C8 alkoxy, and each R ^N Independently a branched, cyclic or linear alkyl or ester group having a molecular weight of 15amu to 100 amu. In other embodiments, longer conjugated pi systems may be used, for example where one or more carbon chains containing alternating double and single bonds are included at the location of the wavy line in the illustrated structure. In other examples longer fused ring systems may be used, e.g. comprising 3, 4 or 5 fused five-membered rings, e.g +. > Wherein each X ² O, S, se, NH, NR independently ^N 、CH ₂ Or C (R) ^N ) ₂ And each W is independently H, F, or branched or straight chain C1-C8 alkyl or branched or straight chain C1-C8 alkoxy. The inclusion of pi moieties in a photoactive compound may, for example, result in a change in the optical properties of the photoactive compound. As an example, a red shift of the absorption maximum can be achieved by longer and longer pi portions between the a and D portions. However, it will be appreciated that the inclusion of pi moieties in a photoactive compound may result in an increase in the molecular weight of the compound as compared to a compound that includes the same a and D moieties but does not include pi moieties. As an example, a single five-membered ring (wherein X ² Pi moiety of N) may cause partitioningThe increase in molecular weight was about 64amu. For X ² For each additional fused five membered ring of N, the molecular weight will increase by about 38amu. For example, comprises two condensed five-membered rings (wherein X ² The pi moiety of N) may increase the molecular weight by about 102amu. In some cases, a red-shifted absorption maximum may be beneficial, although the molecular weight increases and the associated vapor pressure and volatility decrease. In other cases, the red-shifted absorption maximum may not offset the increase in molecular weight and the associated decrease in vapor pressure and volatility.

Without limitation, each "D" moiety in the photoactive compound may be independently selected from:

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when each X is independently O, S, se, NH, NR ^N 、CH ₂ 、C(R ^N ) ₂ 、Si(R ^N ) ₂ Or Ge (R) ^N ) ₂ When each R ^N Independently a branched, cyclic or linear alkyl or ester group having a molecular weight of from 15amu to 100amu, each W is independently H, F, or a branched or linear C1-C8 alkyl or branched or linear C1-C8 alkoxy group, each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, each Z is independently a pendant group (e.g., R ^N ) Or a planarity-disrupting portion, Y ³ Is independently O or S, and Y ⁴ Independently CH, N, or CR ^N 。

Various pendant groups Z may be used. In some examples, one or more Z are independently: substituted (e.g., halogen substituted) or unsubstituted alkyl, substituted (e.g., halogen substituted) or unsubstituted alkenyl, unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted cycloalkyl, unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted cycloalkenyl, unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted cyclopentadienyl, or unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted phenyl. Optionally, Z comprises one or more halogen or trihalomethyl substituents. Alternatively, two Z together form an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted cycloalkyl, an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted cycloalkenyl, an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted cyclopentadienyl, or an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted phenyl. In some embodiments, two Z together form a group comprising: an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted fused five-membered ring, an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted fused six-membered ring, or an unsubstituted or methyl, ethyl, halogen or trihalomethyl substituted fused five-membered and six-membered ring. In some embodiments, two Z together form a heterocyclyl or fused heterocyclyl. Alternatively, one or more Z may be a hydrogen atom. Alternatively, one or more Z may be 2-methylbutyl.

In some cases, each D moiety may include a planar central core having one or more pendant groups Z. In the examples given above, each D moiety may comprise a planar fused ring central core structure comprising an aromatic, heteroaromatic, polycyclic aromatic or polycyclic heteroaromatic moiety comprising one or more five-and/or six-membered rings, wherein the ring structure comprises carbon and optionally one or more heteroatoms. In some cases, the atom to which one or more of the pendant groups Z are bonded is a quaternary center Q. For example, the D portion may compriseWhere Q is a quaternary center, which may be C, si or Ge, for example. The presence of a quaternary center can be used to conformationally lock one or more pendant groups Z in their configuration out of the plane of the central core. In specific examples, the D moiety may comprise one or more of the following groups or heterocyclic analogues thereof:

each of which is unsubstituted or substituted with one or more methyl, ethyl, halogen (e.g., fluorine) or trihalomethyl (e.g., trifluoromethyl) groups or heterocyclic analogs thereof. Although in these examples a single configuration is shown for the various different sizes of the olefin rings, isomers in which the double bond is in different positions are also contemplated herein, e.g.) > (which is optionally substituted with one or more methyl, ethyl, halogen (e.g., fluorine) or trihalomethyl (e.g., trifluoromethyl)) or a heterocyclic analog thereof. As shown, a pendant group including a cyclic group containing a quaternary carbon atom Q may allow the electron donor molecule to assume a spiro structure.

The inclusion of one or more pendant groups Z conformationally locked out of the plane of the central core may provide advantageous properties to the photoactive compound, such as an increase in sublimation yield. For example, a photoactive compound containing a pendent group that is conformationally locked out of the plane of the central core (e.g., a photoactive compound that is nucleus-disrupted) may exhibit a greater vapor pressure and a lower sublimation temperature, e.g., although exhibiting the same, nearly the same, or comparable molecular weights (e.g., within 2 or 3amu of each other) as other compounds containing pendent groups that are not conformationally locked out of the plane of the central core (e.g., photoactive compounds that are nucleus-disrupted). Without wishing to be bound by any theory, including conformationally locking the pendent groups out of the plane of the central core of the photoactive compound may result in a disruption of the volumetric crystal packing efficiency of the photoactive compound, making the crystallized structure less energetically favorable than the photoactive compound having a more closely packed crystal structure. In this way, the core-destroyed photoactive compounds may exhibit relatively little heat of fusion, heat of vaporization, and/or heat of sublimation, such that these compounds relatively readily vaporize into the gas phase. Thus, the sublimation yield of a photoactive compound comprising a pendent group conformationally locked out of the plane of the central core may be greater than the sublimation yield of a similar photoactive compound having a pendent group that is not conformationally locked out of the plane of the central core.

A variety of different photoactive compounds may be formulated and used in accordance with the description above. Some specific exemplary photoactive compounds include those having the formula:

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it will be appreciated that a variety of other photoactive compounds are also contemplated, including various combinations of the disclosed A, D and pi moieties. />

For example, additional photoactive compounds include those of any of the following formulas, e.g., wherein any specified Z group is 2-methylbutyl:

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the disclosed photoactive compounds can be paired with a variety of other compounds to form photovoltaic heterojunctions. For example, when the photoactive compound is an electron acceptor compound, it can be paired with a corresponding electron donor material. As another example, when the photoactive compound is an electron donor compound, it can be paired with a corresponding electron acceptor material. For example, the corresponding electron donor material may be a corresponding electron donor compound, and in some cases may be different from the photoactive materials described herein. For example, the corresponding electron acceptor material may be a corresponding electron donor compound, and in some cases may be different from the photoactive materials described herein. In some cases, the photoactive layer can include one or more different electron donor compounds (e.g., a blend of different photoactive compounds). In some cases, the photoactive layer can include one or more different electron acceptor compounds (e.g., a blend of different photoactive compounds).

In some examples, the photoactive material of the device may comprise a photoactive compound as an electron acceptor compound described herein, and the electron donor compound comprises a boron-dipyrromethene (BODIPY) compound, a phthalocyanine compound, a naphthalocyanine compound, a Metal Dithiolon (MDT) compound, or a dithiophene squaraine compound. Combinations thereof may also be used. Examples of useful BODIPY compounds include, but are not limited to, those described in U.S. patent application No. 16/010,371, filed on date 2018, 6, 15, which is incorporated herein by reference. Examples of useful phthalocyanine and naphthalocyanine compounds include, but are not limited to, those described in U.S. patent application Ser. No. 16/010,365, filed on date 15 at 2018, 6, which is incorporated herein by reference. Examples of useful MDT compounds include, but are not limited to, those described in U.S. patent application Ser. No. 16/010,369, filed on date 2018, 6, 15, which is incorporated herein by reference. Examples of useful dithienosyl phthalocyanine compounds include, but are not limited to, those described in U.S. patent application Ser. No. 16/010,374 filed on date 2018, 6, 15, which is incorporated herein by reference. In some examples, the photoactive layer comprises a BODIPY compound, a phthalocyanine compound, a naphthalocyanine compound, an MDT compound, a dithiophene squaraine compound, or a combination thereof.

Aspects of the invention may be further understood by reference to the following non-limiting examples.

Example 1-Synthesis of example photoactive Compounds including those containing Nuclear destruction and indandione groups

Figures 8 through 34 provide an overview of various exemplary synthetic schemes that provide synthetic routes to various photoactive compounds, including nucleus-disrupted compounds and indandione group-containing compounds.

FIG. 8 provides a synthetic scheme for the preparation of compound III from compound II.

Compound II: flask 1: to a dry three-necked flask, 4H-cyclopenta [1,2-b:5,4-b' ] dithiophene (10.08 g,0.0565 mol) and 240mL of anhydrous THF were charged under nitrogen. The reaction flask was then cooled to-20 ℃ and n-BuLi (2.5M in hexane, 22.4ml,0.056 mol) was added dropwise. The temperature was maintained between-25 ℃ and-18 ℃ for 30 minutes while stirring was performed using a magnetic coupling screw.

Flask 2: in a second three-necked flask, which was dried under nitrogen, 1, 5-dibromopentane was added to 80mL of anhydrous THF, and then cooled to-70℃with dry ice and acetone Dewar flask. The dried addition funnel was added to one of the flask ports and the reaction mixture from flask 1 was cannulated into the addition funnel and added dropwise to flask 2 at-70 ℃ over the course of 30 minutes. The new reaction mixture was stirred at-70 ℃ for 30 minutes and 80mL of anhydrous THF was flushed through the addition funnel to further dilute the reaction. A second equivalent of n-BuLi (2.5M in hexane, 22.4mL,0.056 mol) was added dropwise to the reaction mixture and stirred at-70℃for 30 minutes, then gradually warmed to room temperature over the course of a further 30 minutes. The reaction was continued for 1 hour at room temperature, then worked up by adding to 600mL of deionized water, extracting 3 times with 300mL of diethyl ether, drying over sodium sulfate, and concentrating in vacuo to give the crude product. Purification by column chromatography on Silica-60 with heptane afforded compound II (6.13 g, yield 44%).

Compound III: to a dry three-necked flask under nitrogen protection was added compound II (0.40 g,0.00162 mol) and 40mL of anhydrous diethyl ether. TMEDA was added dropwise to the reaction mixture at room temperature, and the flask was then cooled to-40 ℃. n-BuLi (2.5M in hexane, 1.30mL,0.00325 mol) was added dropwise to the reaction mixture. The reaction mixture was allowed to warm to room temperature over 30 minutes and then mixed at room temperature for an additional 30 minutes. The flask was then cooled to-40℃and anhydrous DMF (0.50 mL,0.00649 mol) was added. The reaction was allowed to mix at-40 ℃ for 30 minutes, then gradually warmed, and mixed overnight at room temperature. By pouring the reaction mixture into 100mL of 20% NH ₄ The post-treatment was completed by extracting 3 times with dichloromethane in Cl (aq) solution and drying over sodium sulfate to give the crude compound III. By Silica-60 column chromatographyPurification by elution with dichloromethane-heptane afforded compound III (0.348 g, 71% yield).

FIG. 9 provides a synthetic scheme for preparing various core-disrupted photoactive compounds:

compound V: to a three-necked flask equipped with a condenser and magnetic stir bar were added compound III (0.15 g,0.0005 mol), compound IV (0.43 g,0.002 mol) and 60mL acetic anhydride. The flask was purged with nitrogen and then stirred at room temperature for 30 minutes, then heated to 90 ℃ and stirred for an additional 1 hour. 200mL of water was added to the cooled reaction, and the precipitate was filtered to obtain compound V. The compound was sublimated in a yield of 5%. Lambda (lambda) _max (DCM):696nm。

Compound VII: to a three-necked flask equipped with a condenser and a magnetic stirring bar were added compound III (1.0 eq), compound VI (4.0 eq) and anhydrous chloroform. The flask was purged with nitrogen and then pyridine (20.0 eq) was added dropwise. The mixture was stirred at room temperature under nitrogen for 30 minutes, then heated to reflux and stirred for 48 hours. The reaction mixture was cooled to room temperature, concentrated in vacuo, and then resuspended in hot isopropanol. The suspension was filtered and washed with additional isopropanol and then dried to obtain compound VII. The compound was sublimated in a yield of 0%. Lambda (lambda) _max (DCM):682nm。

Compound IX: to a three-necked flask equipped with a condenser and a magnetic stirring bar were added compound III (1.0 eq), compound VIII (4.0 eq) and anhydrous chloroform. The flask was purged with nitrogen and then pyridine (20.0 eq) was added dropwise. The mixture was heated to reflux under nitrogen and stirred for 18 hours. The reaction mixture was cooled to room temperature and then poured into 200mL of cold methanol. The suspension was filtered and then washed with additional methanol to give compound IX as a bright green solid with limited solubility in 80% yield. The compound was sublimated in a yield of 30%. Lambda (lambda) _max (DCM):609nm。

Compound XI: using the same method as for compound IX, using the compound X is substituted for compound VIII and compound XI is synthesized from compound III. Sublimating the compound XI, yield 13%. Lambda (lambda) _max (DCM):676nm。

FIG. 10 provides a synthetic scheme for preparing various core-disrupted photoactive compounds:

compound XIII: compound XIII was synthesized from compound III using the same method as for compound IX, substituting compound XII for compound VIII. Sublimating compound XIII with a yield of 65% -85%. Lambda (lambda) _max (DCM):593nm。

Compound XV: compound XV was synthesized from compound III in 73% yield using the same procedure as for compound IX, substituting compound XIV for compound VIII. Sublimating the compound XV, the yield was 9%. Lambda (lambda) _max (DCM):611nm。

Compound XVII: compound XVII was synthesized from compound III using the same procedure as for compound VII, substituting compound XVI for compound VI, in 99% yield. Sublimating the compound with a yield of 75% -88%. Lambda (lambda) _max (DCM):599nm。

FIG. 11 provides a synthetic scheme for preparing a core-disrupted photoactive compound:

compound XVIII was synthesized from compound I in 55% yield using the same procedure as for compound II, substituting 1, 5-pentandiol, 3-dimethyl-, 1, 5-dimethyl sulfonate for 1, 5-dibromopentane.

Compound XIX was synthesized in 51% yield using the same method as for compound III, substituting compound XVIII for compound II.

Compound XX was synthesized from compound VIII using the same method as for compound IX, substituting compound XIX for compound III, in a yield of 41%. Sublimating compound XX, yield was 12%.

FIG. 12 provides a synthetic scheme for preparing a core-disrupted photoactive compound:

compound XXI was synthesized from compound I in 69% yield using the same method as for compound II, substituting 1, 4-dibromobutane for 1, 5-dibromopentane.

Compound XXII was synthesized in 39% yield using the same method as for compound III, substituting compound XXI for compound II.

Compound XXIII is synthesized from compound VIII using the same method as for compound IX, substituting compound XXII for compound III. Sublimating compound XXIII in 12% yield. Lambda (lambda) _max (DCM):686nm。

FIG. 13 provides a synthetic scheme for preparing a core-disrupted photoactive compound:

compound XXIV was synthesized from compound I using the same method as for compound II, substituting 1, 4-butanediol, 2, 3-dimethyl-sulfonate for 1, 5-dibromopentane, in 53% yield.

Compound XXV was synthesized in 51% yield using the same method as for compound III, substituting compound XXIV for compound II.

Compound XXVI was synthesized from compound VIII using the same method as for compound IX, substituting compound XXV for compound III, in 93% yield. Sublimating compound XXVI in 5% yield. Lambda (lambda) _max (DCM):680nm。

FIG. 14 provides a synthetic scheme for the preparation of compound XXVIII from compound XXVII.

Compound XXVII: into a dry three-necked flask, under a nitrogen atmosphere, compound I (9 g,0.050 mol), potassium hydroxide (9.06 g,0.162 mol) and250mL of anhydrous DMSO. The reaction flask was purged with nitrogen and magnetically stirred at room temperature for 45 minutes. Bromoethane (11.0 g,0.101 mol) was added dropwise, and the mixture was stirred for 18 hours. The reaction mixture was diluted with ethyl acetate, then washed with water, then with saturated sodium chloride solution. Anhydrous MgSO for organic layer ₄ Dried, filtered and concentrated in vacuo to give the crude product as an oil. Purification was achieved by Silica-60 column chromatography eluting with a heptane/ethyl acetate gradient to give compound XXVII as an oil (11 g) in 93% yield.

Compound XXVIII was synthesized in 79% yield using the same method as for compound III, substituting compound XXVII for compound II.

FIG. 15 provides a synthetic scheme for the preparation of various photoactive compounds:

Compound XXIX was synthesized from compound X using the same method as for compound XI, substituting compound XXVIII for compound III. Lambda (lambda) _max (DCM):477nm。

Compound XXX was synthesized in 73% yield using the same procedure as for compound V, substituting compound XXVIII for compound III and compound VIII for compound IV. Lambda (lambda) _max (DCM):676nm。

Compound XXXI: to a three-necked flask equipped with a condenser and a magnetic stirring bar were added compound XXVIII (0.5 g,0.002 mol), compound VI (1.59 g, 0.0070 mol) and 150mL of anhydrous chloroform. The flask was purged with nitrogen and then pyridine (1.63 g,0.021 mol) was added dropwise. The mixture was stirred at room temperature under nitrogen for 30 minutes, then heated to reflux and stirred for 18 hours. The reaction mixture was cooled to room temperature and then poured into cold water. The biphasic mixture was extracted with dichloromethane. The organic layers were combined, dried over MgSO ₄ Dried, filtered and concentrated in vacuo to afford compound XXXI (1.2 g,98% yield) as a dark solid. Lambda (lambda) _max (DCM):614nm。

Compound XXXII was synthesized using the same procedure as for compound IX, substituting compound XXVIII for compound III and compound XII for compound VIII. Sublimating compound XXXII, yield 30%.

FIG. 16 provides a synthetic scheme for preparing indandione containing photoactive compounds:

Compound XXXIII was synthesized from compound I in 90% yield using the same procedure as for compound XXXVII, substituting 1-chloro-2-methylbutane for 1, 5-dibromopentane.

Compound XXXIV was synthesized in 84% yield using the same procedure as for compound III, substituting compound XXXIII for compound II.

Compound XXXV: a solution of compound XXXIV (6.37 g,17.0mmol,1 eq.) and XVI (12.38 g,68.0mmol,4 eq.) in chloroform (640 mL,100 vol) is flushed with nitrogen for 5 min. Pyridine (20.6 mL,20.2g,255mmol,15 eq.) was slowly added over 2 minutes. The solution was then heated at 60 ℃ (reflux) for 30 hours. The suspension was cooled to 23℃and filtered through a pad of celite (18 g), rinsing with dichloromethane (3X 100 mL). The combined filtrates were concentrated to dryness under reduced pressure to give a crude dark solid (18 g). The solid was suspended in dichloromethane (450 mL) for 1 hour at 40 ℃ (reflux) and filtered through a celite pad (18 g), rinsing with dichloromethane (2×100 mL). The filtrate was concentrated under reduced pressure to a volume of 200mL. The solution was heated at 40 ℃ and slowly treated with hexane (360 mL) over 1.5 hours. The suspension was cooled to 23 ℃ over 2 hours, the solids were collected by vacuum filtration and extracted with hexane and dichloromethane 2:1 mixture (3X 50 mL). The filtrate was concentrated onto celite (26 g) and purified on an automated Biotage system (Sorbtech 330g column) eluting with a gradient of 50% -100% dichloromethane/heptane to give compound XXXV (5.3 g) in 44% yield. Sublimating the compound with a yield of 60% -80%.

FIG. 17 provides a synthetic scheme for preparing core-disrupted indandione-containing photoactive compounds:

compound XXXVI: compound II (2.5 g,1.0 eq) was dissolved in 67mL chloroform, then NBS (3.97 g,2.2 eq) was added and the mixture was stirred in the dark for 12 hours. After completion, the reaction mixture was poured into water, and the biphasic mixture was extracted with chloroform. The organic layers were combined, using MgSO ₄ Dried, filtered and concentrated. The crude material was dry loaded onto silica gel and purified by CombiFlash. The desired product was eluted with heptane to give compound XXXVI (3.68 g,89% yield) as an orange solid.

Compound XXXVII: in an oven-dried three-neck RB flask equipped with a nitrogen inlet, diisopropylamine (2.65 g,4.0 eq) was dissolved in dry THF (30 mL), the reaction temperature was adjusted to-78 ℃, then n-butyllithium (2.5 m,9.8mL,4.0 eq) was added dropwise, and the reaction was stirred at 0 ℃ for 30 minutes to yield LDA. In another oven-dried 100mL three-necked RB flask, compound XXXVI was dissolved in dry THF (15 mL), the reaction temperature was adjusted to-78℃and LDA formed in the other RB flask was then added dropwise. The mixture was stirred at this temperature for 30 minutes, then warmed to room temperature and held for 2 hours. After cooling the mixture to 0deg.C, anhydrous DMF (1.2 mL) was added and the reaction was stirred at this temperature for 30 minutes. The mixture was then warmed to room temperature for 1 hour and water (30 mL) was added. The organics were extracted (3×30mL DCM), dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography eluting with DCM/heptane using a 24g column to give compound XXXVII as a yellow solid (1.1 g,47% yield).

Compound XXXVIII: in an oven-dried 100mL three-necked RB flask equipped with a nitrogen inlet, ethyl thioglycolate (0.9 g,2.0 eq) was added dropwise to a mixture of compound XXXVII (1.4 g,1.0 eq) and potassium carbonate (1.5 g,3.0 eq) in DMF (10 mL) at 50℃under argon. After addition, the mixture was stirred at this temperature for 24 hours. TLC (DCM) showed the reaction was complete. The reaction was quenched by the addition of water (50 mL). The yellow precipitate was filtered and purified by column chromatography on silica eluting with heptane/DCM. The appropriate fractions were combined, concentrated, and dried under high vacuum to give compound XXXVIII (1.05 g,72% yield).

Compound XXXIX: lithium aluminum hydride (0.30 g,3.5 eq.) was suspended in 15mL THF and cooled to 0deg.C, then compound XXXVIII (1.05 g,1.0 eq.) dissolved in 30mL THF was added dropwise. The residue in the vial was rinsed and transferred with an additional 10mL THF. The reaction was warmed to room temperature and stirred overnight. The reaction was cooled to 0 ℃ and quenched by slow addition of water. The biphasic mixture was extracted with diethyl ether. The organic layers were combined, washed with brine, and dried over MgSO ₄ Dried, filtered and concentrated to give a brown solid/foam. The crude material was purified by column chromatography and purified with heptane: etOAc eluted to give compound XXXIX as a pale yellow solid (0.762 g,94% yield).

Compound XL: compound XXXIX (610 mg,1.0 eq) is added to a dry 100mL three-necked flask followed by 50mL of anhydrous DCM. DMP (dess-martin periodate) (1.9 g,2.6 eq.) was added in portions and the reaction stirred under nitrogen overnight. The reaction mixture was diluted with diethyl ether and sequentially with 1N NaOH, 1M Na ₂ S ₂ O ₃ Washed with saturated bicarbonate and brine. MgSO for organic layer ₄ Dried, filtered and concentrated. The crude material was dry loaded onto silica gel and purified by column chromatography. The desired product was eluted with heptane/EtOAc to give compound XL (343 mg,57% yield) as a yellowish-brown solid.

Compound XLI: compound XL (200 mg,1.0 eq) was added to a 100mL three-necked flask followed by compound XVI (280 mg,4.0 eq) and 40mL DCE. The mixture was purged with nitrogen at room temperature for 20 minutes, then pyridine (0.85 ml,12.0 eq) was added dropwise. The reaction was stirred at room temperature for an additional 20 minutes, then heated to reflux and stirred for 96 hours. The precipitate was filtered and washed with hot methanol to give compound XLI (120 mg, 49%). The compound was sublimated in a yield of 9%. Lambda (lambda) _max (DCM):610nm。

FIG. 18 provides a synthetic scheme for preparing a core-disrupted indandione-containing photoactive compound that includes a thiophene pi moiety:

Compound XLII: in an oven-dried 250mL three-necked RB flask, compound II (1.5 g,1.0 eq.) was dissolved in dry THF (70 mL) under nitrogen, the reaction temperature was adjusted to-78deg.C, and then n-butyllithium (2.5M, 5.1mL,2.1 eq.) was added dropwise. The reaction mixture was then stirred at-10 to 0 ℃ for 1 hour, then readjusted to-78 ℃ before trimethyltin (1M solution, 18.3ml,3.0 eq.) was added dropwise. The reaction mixture was then stirred at room temperature. After 18 hours, the reaction was quenched by the addition of water. The organic layer was separated and the aqueous layer was washed with diethyl ether (2X 50 mL). The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give compound XLII, which was used as such in the next step.

Compound XLIII: in a 250mL three-necked RB flask equipped with a nitrogen line and condenser, compound XLII (3.5 g,1.0 eq) and compound 5-bromo-thiophene-2-carbaldehyde (2.34 g,2.0 eq) were dissolved in dry toluene (200 mL) under nitrogen, the solution was purged with nitrogen for 30 minutes, then Pd (PPh) was added ₃ ) ₄ (0.7 g,0.10 eq). The mixture was purged with nitrogen and refluxed for 18 hours. TLC showed that two yellow/red spots of lower Rf formed. The reaction mixture was concentrated in vacuo and purified by autoprep chromatography using 80g silica gel column with DCM/EtOAc to give compound XLIII (1.7 g,60% yield).

Compound XLIV: in an oven-dried 500mL three-necked RB flask equipped with a condenser and nitrogen inlet, compound XLIII (0.5 g,1.0 eq), compound XVII (1.0 g,5.0 eq) and ammonium acetate (1.65 g,20.0 eq) were dried over dichloroethane (200 mL) under nitrogen and the reaction mixture was refluxed at 83℃for 3 weeks. The reaction mixture was cooled to room temperature and the dark green solid was filtered. The resulting solid was washed with hot methanol and dried under high vacuum to give compound XLIV (0.85 g,100% yield). Sublimating the compound with a yield of 12% -17%. Lambda (lambda) _max (DCM):654nm。

FIG. 19 provides a synthetic scheme for preparing core-disrupted indandione-containing photoactive compounds:

compound XLV was synthesized from compound XLII in 19% yield using the same method as for compound XLIII, substituting 5-bromo-thiophene-2-carbaldehyde with 5-bromo-4-butyl-thiophene-2-carbaldehyde.

Compound XLVI was synthesized from compound XVI in 100% yield using the same method as for compound XVII, substituting compound XLV for compound III. The compound was sublimated in a yield of 3%. Lambda (lambda) _max (DCM):640nm。

FIG. 20 provides a synthetic scheme for preparing a core-disrupted photoactive compound:

compound XLVIII: compounds XLII (1.0 eq), XLVIII (2.1 eq) and Pd (PPh) were reacted under nitrogen ₃ ) ₄ (0.1 eq.) was added to dry toluene and the mixture was purged with nitrogen. The reaction mixture was then stirred at 110℃for 24 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography using methylene chloride to obtain compound XLVIII.

Compound L was synthesized from compound XLII using the same method as for compound XLVIII, substituting compound XLIX for compound XLVIII.

Figure 21 provides a synthetic scheme for the preparation of compound LII by compound LI.

Compound LI: 3,3 '-dibromo-2, 2' -dithiophene (15 g,1.0 eq), sodium tert-butoxide (10 g,2.2 eq), pd ₂ (dba) ₃ (1.26 g,0.03 eq) and BINAP (3.45 g,0.12 eq) in anhydrous toluene were purged with nitrogen for 30 minutes, then 2-methylbutylamine (4.05 g,1.0 eq) was added and the reaction mixture was refluxed under nitrogen atmosphere at 110℃for 48 hours. The reaction mixture was then poured into water and extracted with dichloromethane (200 mL)Taking. The organic layer was separated, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by flash chromatography to give compound LI (9.6 g,76% yield).

Compound LII: to a dry three-necked flask was added compound LI (4.3 g,1.0 eq) and dissolved in anhydrous THF under nitrogen atmosphere followed by TMEDA (5.21 g,2.6 eq). N-butyllithium (2.5M, 18mL,2.6 eq) was then added dropwise and the reaction mixture was stirred for an additional 30 minutes at-40℃and then warmed to room temperature, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was cooled back to-40 ℃, then dry DMF (3.27 g,2.6 eq) was added dropwise and stirred at room temperature overnight. By pouring the reaction mixture into 20% NH ₄ The Cl (aq) solution was extracted 3 times with dichloromethane and dried over sodium sulfate to give the crude product for finishing the work-up. Purification by silica gel column chromatography using methylene chloride-heptane gave compound LII (2.5 g, yield 62%).

FIG. 22 provides a synthetic scheme for the preparation of various photoactive compounds:

compound LIII: compound LII (1.0 equivalent) and compound X (4.0 equivalent) were mixed with anhydrous chloroform under nitrogen atmosphere, followed by addition of pyridine (20 equivalents). The reaction mixture was refluxed for 48 hours and then cooled to room temperature. The precipitate was filtered and washed with hot isopropanol to give compound IV (60% yield).

Compound LIV was synthesized from the LII compound in 90% yield using the same method as for compound LIII, substituting compound VIII for compound X.

Compound LVI was synthesized from compounds LII and LV in 75% yield using a similar procedure as for compound LIII, substituting compound LV for compound X.

FIG. 23 provides a synthetic scheme for preparing photoactive compounds:

compound LVIII: a suspension of compound LVII (1 equivalent), potassium hydroxide (7.5 equivalents) and potassium iodide (0.04 equivalent) in anhydrous dimethyl sulfoxide (25 vol) was purged with nitrogen for 5 minutes. 1-chloro-2-methylbutane (4.6 eq.) was slowly added over 10 minutes under nitrogen. The resulting dark suspension was stirred at 21 ℃ for 18 hours. The reaction mixture was cooled to 10 ℃. Water (25 vol) (T) was added dropwise over 5 minutes _max =14℃). The mixture was then further diluted with water (25 vol) and extracted into heptane (60 vol, then 2 x 30 vol). The organics were combined, washed with water (25 vol), dried (Na ₂ SO ₄ ) And filtered. The filtrate was concentrated in vacuo to give the crude product as a dark brown oil. By flash column chromatography (SiO ₂ ) Purification by heptane elution afforded compound LVIII as a yellow oil (67% yield) as a set.

Compound LIX: to an oven-dried flask containing a solution of DMF (20 equivalents) in DCE (15 vol) was added dropwise phosphorus oxychloride (20 equivalents) over 20 minutes under a nitrogen atmosphere. The resulting yellow solution was stirred at ambient temperature for 3 hours. Then a solution of compound LVIII (1 equivalent) in dichloroethane (37.5 vol) was added dropwise over 15 minutes (no exotherm was observed). The solution was then heated to 60 ℃ for 42 hours and then cooled to room temperature. The solvent was removed on a rotary evaporator. The resulting brown gum was quenched with ice water (25 vol) and then basified with saturated sodium bicarbonate solution to about pH8. The resulting suspension was then stirred at room temperature for 2 hours and then extracted into DCM (50 vol, then 2×25 vol). The organics were dried (Na ₂ SO ₄ ) And concentrated in vacuo to afford compound LIX as a brown solid (72%).

Compound LX: a solution of compounds LIX (1 eq) and XVI (4 eq) in chloroform (56 vol) was flushed with nitrogen for 5 minutes. Pyridine (15 equivalents) was then added to raise the temperature by 15.5 ℃ to 17.5 ℃. The mixture was then heated to reflux. After 48 hours, the dark purple reaction solution was cooled to room temperature. A small sample was taken, concentrated, and analyzed by 1HnmR spectroscopy, indicating that all aldehydes were consumed. The reaction mixture was concentrated on a rotary evaporator to give the crude product as a dark purple solid, which was further purified by washing with hot methanol to give compound LX (90%). The compound was sublimated in a yield of 65%.

Compound LXI and compound LXII were synthesized using the same method as for compound LX, but using different reagents instead of 1-chloro-2-methylbutane (e.g., methyl chloride or p-chlorotoluene) and instead of compound XVI (e.g., compound X):

FIG. 24 provides a synthetic scheme for the preparation of compound LXIV from compound LXIII.

Compound LXIII: n-butyllithium (2.0 eq) was added to dry THF in a two-necked RB flask, the reaction mixture was cooled to-78 ℃, then 3,3 '-dibromo-2, 2' -bithiophene (1.0 eq) dissolved in THF was added dropwise, and the reaction mixture was stirred for 1 hour. A solution of dichlorosilane (1.1 eq.) in THF was added to the reaction mixture, maintaining the reaction temperature below-70 ℃. After addition, the reaction mixture was stirred at room temperature overnight. The reaction was then quenched by addition of aqueous ammonium chloride, the product extracted with diethyl ether and purified by column chromatography using heptane. The product after chromatography is distilled and purified under reduced pressure at 390 ℃ to obtain the compound LXIII with the yield of 12 percent.

Compound LXIV: phosphorus oxychloride (10 eq.) was added dropwise over 20 minutes to an oven dried flask of DCE solution containing DMF (20 eq.) at 0 ℃ under nitrogen atmosphere. The resulting yellow solution was stirred at ambient temperature for 3 hours. A solution of compound LXIII (1 eq.) in dichloroethane was then added dropwise over 15 minutes. The solution was then heated to 90 ℃. After 4 hours, the reaction mixture was cooled to room temperature and poured into saturated sodium acetate solution under ice bath. The product was extracted with dichloromethane. The organic layer was dried over sodium sulfate, concentrated in vacuo, and purified by column chromatography to give compound LXIV in 60% yield.

FIG. 25 provides a synthetic scheme for preparing various core-disrupted photoactive compounds:

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compound LXV: compounds LXIV (1.0 eq.) and X (4.0 eq.) were refluxed with pyridine (15.0 eq.) and chloroform for 48 hours. The reaction mixture was filtered while it was still hot, and the precipitate was washed with chloroform to give compound LXV in 82% yield. The compound was sublimated in a yield of 7%.

Compound LXVI was synthesized from compound LXIV using a similar method as for compound LXV, substituting compound VIII for compound X. Sublimating the compound LXVI, the yield was 10%.

Compound LXVII: compounds LXIV (1.0 eq) and LV (4.0 eq) were mixed with acetic anhydride and the mixture was degassed with nitrogen. The reaction mixture was then stirred at 50℃for 15 minutes and then at 80℃for 4 hours. The reaction mixture was then cooled to room temperature and filtered. The precipitate was washed with heptane and triturated with dichloromethane/methanol (8/2) to give compound LXVII (82%). The compound was sublimated in a yield of 11%.

Compound LXVIII was synthesized from compound LV using the same method as for LXVII, substituting compound III for compound LXIV. Sublimating compound LXVIII in 31% yield:

FIG. 26 provides a synthetic scheme for preparing photoactive compounds:

compound LXIX: to a three-necked flask was added benzo [1,2-b:4,5-b ]']Dithiophene-4, 8-dione, zinc, sodium hydroxide and 126mL of water. Will be mixedThe mixture was refluxed for 3 hours and then cooled to room temperature. Bromoethane (4.45 g,0.041 mol) and tetrabutylammonium bromide (0.44 g,0.001 mol) were added and the reaction was refluxed for an additional 6 hours. The reaction was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The organic layers were combined, using MgSO ₄ Drying, filtration and concentration in vacuo gave the crude product as an oil. Purification by Silica-60 column chromatography using a heptane/dichloromethane gradient afforded compound LXIX (2.37 g,63% yield).

Compound LXX was synthesized in 20% yield using the same method as for compound III, substituting compound LXIX for compound II.

Compound LXXI was synthesized from compound VIII in 80% yield using the same method as for compound IX, substituting compound LXX for compound III. Sublimating the compound LXIXI in 0% yield. Lambda (lambda) _max (DCM):494nm。

FIGS. 27-34 provide an overview of various exemplary synthetic schemes that provide synthetic routes to various photoactive compounds, including indandione-containing compounds. FIG. 27 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound LXXIII: in a 2L three-necked flask, which was oven-dried and equipped with a nitrogen inlet and a condenser, compound LXII (30.0 g,0.053 mol), sodium t-butoxide (51.12 g,0.005 mol), pd (dba) was introduced into a flask ₂ A solution of (3.06 g,0.005 mol) and dppf (11.80 g,0.021 mol) in 900mL of anhydrous toluene was stirred at room temperature under nitrogen for 20 minutes. After the addition of 2-methylbutylamine (13.91 g,0.532 mol), the mixture was stirred at 110℃for 20 hours. The reaction was cooled to room temperature and then diluted with water. The biphasic mixture was extracted with DCM. The organic layers were combined, dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by automatic flash chromatography using 330g+125g (stacked) silica gel column eluting with heptane/DCM to give the product as a white foam (10.3 g,47% yield).

Compound LXXIV: DMF (31 g,0.4 mol) and POCl ₃ A mixture of (65 g,0.4 mol) in 250mL of dichloroethane was stirred at room temperature for 2 hours. Compound LXIII (7.0 g,0.017 mol) dissolved in 1.2L DCE was added and the mixture was stirred at 60℃for 4 days. TLC and LC-MS after small post-treatment showed the reaction was complete. The reaction mixture was concentrated under vacuum and the residue was neutralized/hydrolyzed with saturated sodium bicarbonate until the pH was neutral. The red precipitate was filtered and washed with water. The wet crude material was stirred with DCM (700 mL) and dried over sodium sulfate. The DCM solution was concentrated and slurried on silica gel (-40 g) and purified by automatic flash chromatography using a 330g column eluting with DCM/EtOAc (0-20%). The appropriate fractions were combined and concentrated to give compound III as an orange solid (7.2 g, 90%).

Compound LXXV: compound LXXIV (1.5 g, 0.003mol), compound XVI (2.9 g,0.016 mol) and ammonium acetate (3.68 g,0.048 mol) were dissolved in 800mL of dichloroethane in an oven-dried 250mL three-necked flask equipped with a condenser and a nitrogen inlet under an argon atmosphere. The solution was refluxed for 72 hours. The reaction mixture was filtered hot and the green precipitate was washed with hot methanol to afford the desired product (200 mg,42% yield). The compound was sublimated in a yield of 38%. Lambda (lambda) _max (DCM):658nm。

FIG. 28 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound LXVI: compound LXII (6.0 g,10.6mmol,1.0 eq.), sodium tert-butoxide (12.3 g,127mmol,12 eq.), pd (dba) ₂ A mixture of (730 mg,1.27mmol,0.12 eq.) and dppf (2.95 g,5.32mmol,0.5 eq.) in toluene (220 mL) was purged with argon at room temperature for 30 min. 2-ethylhexyl amine (7.0 mL,42.6mmol,4 eq.) was added and the mixture heated at 110deg.C for 20 hours. After cooling to room temperature, the reaction was diluted with water (100 mL). The aqueous layer was separated and extracted with dichloromethane (2X 100 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. Sucking the crude materialAttached to celite (60 g) and purified on a Buchi automated chromatography system (Sorbech silica gel column, 330 g) eluting with a gradient of 0 to 30% dichloromethane in hexane to give the product as a pale yellow solid (2.1 g, 40% yield).

Compound LXVII: compound LXXVII was prepared as described in the synthesis of compound LXXIV, substituting compound LXXVI for compound LXXIII. The product was obtained in 86% yield.

Compound LXVIII: compound LXXVIII was prepared as described in the synthesis of compound LXXV, substituting compound LXXVII for compound LXXIV. The product was obtained in 74% yield. The compound was sublimated in a yield of 10%. Lambda (lambda) _max (DCM):658nm

FIG. 29 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound LXXIX: a suspension of compound LXII (15.55 g,27.57mmol,1 eq.) bis (dibenzylideneacetone) palladium (1.59 g,2.76mmol,0.1 eq.), 1' -bis (diphenylphosphino) ferrocene (6.11 g,11.0mmol,0.4 eq.) and sodium tert-butoxide (42.4 g, 4471 mmol,16 eq.) in toluene (180 mL,12 vol) was sparged with nitrogen for 10 minutes. The suspension was then stirred under nitrogen at 23 ℃ for 20 minutes. Then under nitrogen, isopentylamine (6.25 g,8.32mL,71.68mmol,2.6 eq.) was added. The resulting suspension was heated at 104℃for 16 hours. The suspension was cooled to 23 ℃ and slowly treated with ice water (100 mL). The two-phase mixture was filtered through a pad of celite (20 g) and the layers were separated. The organic layer was concentrated under reduced pressure. The celite pad was rinsed with methylene chloride (3X 100 mL). The dichloromethane filtrate was combined with the above crude product and concentrated onto celite (22 g). The solid was purified on an intel automated chromatography system (330 g Sorbtech), eluting with a 10% to 20% dichloromethane in heptane gradient to yield a yellow solid (4.9 g). The material was triturated with methanol (20 mL) at 23 ℃ for 2 hours and the solid collected by vacuum filtration, rinsed with methanol (2 x 5 mL) and dried under vacuum at 23 ℃ for 15 hours to give the product as a pale yellow solid (4.86 g, 42% yield).

Compound LXXX: compound LXXX was prepared as described in the synthesis of compound LXXIV, substituting compound LXXIX for compound LXXIII (3.97 g,75% yield).

Compound LXXXI: compound LXX (1.50 g,3.19 mmol) is dissolved in dichloroethane (175 mL) at 75deg.C. Sodium sulfate (5 g) was added. The suspension was kept at 75℃for 20 min and filtered hot into a 1L three-necked round bottom flask, rinsed with hot dichloroethane (75 ℃, 3X 100 mL). To the reaction was added 5, 6-difluoro-1H-indene-1, 3 (2H) -dione (2.90 g,15.9mmol,5 eq.), ammonium acetate (3.69 g,47.85mmol,15 eq.) and additional dichloroethane (275 mL). The solution was then heated at 81 ℃ (reflux) for 68 hours. Additional 5, 6-difluoro-1H-indene-1, 3 (2H) -dione (1.16 g,6.38mmol,2 eq.) and ammonium acetate (1.48 g,19.1mmol,6 eq.) were added. The suspension was heated at 81 ℃ (reflux) for 42 hours. The suspension was cooled to 23 ℃ over 2 hours and the solids were collected by vacuum filtration and rinsed with hot methanol (60 ℃,3 x 30 mL). The solid (3.97 g) was triturated with chloroform (400 mL) at 23℃for 20 hours. The solid was collected by vacuum filtration, rinsed with chloroform (3×20 mL) and further dried in a vacuum oven at 50 ℃ for 5 hours to give the product as a dark green solid in quantitative yield. The compound was sublimated in a yield of 23%.

FIG. 30 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound LXXXII: to a solution of compound LXXVI (1.3 g,2.61mmol,1.0 eq.) in anhydrous THF (60 mL) was added dropwise a 2.5M solution of n-butyllithium in hexane (3.1 mL,7.82mmol,3 eq.) over 15 min at-78 ℃. After stirring for 2 hours, 1M solution of trimethyltin chloride in THF (10.5 mL,10.5mmol,4 eq.) was added dropwise over 15 minutes. After stirring for 30 minutes, the reaction was slowly warmed to room temperature and stirred overnight. The reaction was quenched with ice water (20 mL) and extracted with diethyl ether (3X 50 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was dried in vacuo at 25 ℃ for 5 hours to give compound XII as a light brown oil (2.1 g, quantitative yield).

Compound LXXXIV: a mixture of compound LXXXII (1.3 g,1.58mmol,1.0 eq.) compound LXXXII (1.6 g,4.74mmol,3 eq.), tetrakis-triphenylphosphine palladium (185 mg,0.16mmol,0.1 eq.) and copper (I) iodide (30 mg,0.16mmol,0.1 eq.) in toluene (16 mL) was purged with argon at room temperature for 15 minutes. After heating at 110 ℃ overnight, the reaction was cooled to room temperature and concentrated under reduced pressure. The crude material was adsorbed onto celite (40 g) and purified on a Buchi automatic chromatography system (Sorbech silica gel column, 120 g), eluting with a 20% to 100% dichloromethane gradient in hexane. The pure fractions were combined, concentrated and the resulting solid was dried under vacuum overnight at 50 ℃ to give compound LXXXIV as a brown solid (970 mg,60% yield). The compound was sublimated in a yield of 0%. Lambda (lambda) _max (DCM):707nm。

FIG. 31 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound LXXXV: a solution of compound LXII (10 g,17.73mmol,1.0 eq), cyclohexylmethylamine (4.41 g,39.00mmol,2.2 eq.), sodium tert-butoxide (10.22 g,10.64mmol,6.0 eq.) and 1,1' -bis (diphenylphosphino) ferrocene (0.20 g,0.36mmol,0.02 eq.) in anhydrous toluene (80.0 mL) was purged with nitrogen for 20 minutes. Bis (diphenylphosphino) -ferrocene-palladium dichloride-dichloromethane adduct (2.90 g,3.55mmol,0.2 eq.) was added and the mixture stirred at 90 ℃ for 17 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure, diluted with saturated ammonium chloride (100 mL), and extracted with dichloromethane (2×500 mL). The combined organic layers were washed with saturated brine (200 mL), and after adding celite (100 g), concentrated under reduced pressure. The resulting kieselguhr mixture was purified on a Biotage automatic chromatography system (Sorbech 330g,60 μm silica gel column), eluting with a gradient of 0 to 30% dichloromethane in hexane. The product fractions were pooled, concentrated and again chromatographed using a Biotage automatic chromatography system (Sorbtech 330g,60 μm silica gel column), eluting with a 10% to 20% dichloromethane gradient in hexane. The product was dried under vacuum at 50 ℃ overnight to give compound XV (2.73 g,33% yield) as an off-white solid. Further trituration of the crude material with methanol afforded the pure product as a beige solid (1.502 g,87% recovery).

Compound LXXXVI: compound LXXXVI is synthesized using the same method as described for the preparation of compound LXXIV, substituting compound LXXXV for compound LXXIII. The product was obtained in 91% yield.

Compound LXXXVII: compound LXXII was synthesized using the same method as described for the preparation of compound LXXV, substituting compound LXXXVI for compound LXXIV. The compound was sublimated in a yield of 14%.

FIG. 32 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound LXXXVIII: a solution of compound LXII (8.6 g,15.2mmol,1 eq.) and pentan-2-amine (5 mL,45.5mmol,3 eq.) in toluene (200 mL) was purged with nitrogen for 15 min. Meanwhile, pd (dba) was added to another flask ₂ A mixture of (0.9 g,1.5mmol,0.1 eq.) and dppf (3.4 g,6.1mmol,0.4 eq.) in toluene (100 mL) was purged with nitrogen for 15 minutes and transferred to the first mixture via cannula. Sodium tert-butoxide (14.5 g,152mmol,10 eq.) was added to the mixture. After refluxing for 20 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in dichloromethane (300 mL) and washed with water (250 mL). The aqueous layer was extracted with dichloromethane (2X 150 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was adsorbed onto celite (120 g) and purified on an intel automated chromatography system (Sorbtech 220g silica gel column), eluting with a 0 to 20% dichloromethane gradient in hexane to give the product as a yellow solid (1.6 g, 26% yield).

Compound LXXXIX: compound LXXXIX is synthesized using the same method as described for the preparation of compound LXXIV, substituting compound LXXXVIII for compound LXXIII. The product was obtained in 95% yield.

Compound XC: compound XC was synthesized using the same method as described for the preparation of compound lxxxv, substituting compound LXXXIX for compound LXXIV. The product was obtained in 47% yield. The compound was sublimated in 48% yield. Lambda (lambda) _max (DCM):659nm。

FIG. 33 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound XCI: in a 2L three-necked flask, which was oven-dried and equipped with a nitrogen inlet and a condenser, compound LXII (3.0 g,0.005 mol), sodium t-butoxide (5.11 g,0.053 mol), pd (dba) was introduced into a flask ₂ A solution of (0.31 g,0.001 mol) and dppf (1.18 g, 0.002mol) in 90mL of anhydrous toluene was stirred at room temperature under nitrogen for 20 minutes. After the addition of 4, 4-trifluoro-2-methylbutan-1-amine hydrochloride (2.83 g,0.016 mol), the mixture was stirred at 110℃for 20 hours. The reaction was cooled to room temperature and then diluted with water. The biphasic mixture was extracted with DCM (100 mL). The organic layers were combined, dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by automatic flash chromatography using an 80g silica gel column eluting with heptane/DCM. The product was obtained as a yellow solid (1.08 g,39% yield).

Compound XCII: compound XCII was synthesized using the same method as described for the preparation of compound LXXIV, substituting compound XCI for compound LXXIII. The product was obtained in 88% yield.

Compound XCIII: compound XCIII was synthesized using the same procedure as described for the preparation of compound LXXV, substituting compound XCII for compound LXXIV. The product was obtained in quantitative yield. The compound was sublimated in 52% yield. Lambda (lambda) _max (DCM):644nm。

FIG. 34 provides a synthetic scheme for preparing indandione containing photoactive compounds:

compound XCIV: compound LXXIV (2.05 g, 0.04 mol), compound XII (3.18 g,0.022 mol) and ammonium acetate (5.04 g,0.065 mol) were dissolved in 500mL of dichloroethane in an oven-dried 1L three-necked flask equipped with a condenser and a nitrogen inlet under a nitrogen atmosphere. The solution was refluxed for about 48 hours and then cooled to room temperature. The green precipitate was filtered off and washed with hot methanol to give the desired product (1.6 g,50% yield). The filtrate was concentrated in vacuo and the residue was washed with a hot mixture of methanol (100 mL) and DCE (50 mL). The green solid obtained was dried under high vacuum at 60 ℃ overnight to give additional product (1.75 g,55% yield). The compound was sublimated in 40% yield. Lambda (lambda) _max (DCM):646nm。

Compound XCVI: compound LXXIV (1.0 g,0.002 mol), compound XCV (2.27 g,0.01 mol) and ammonium acetate (4.09 g,0.053 mol) were dissolved in 700mL of dichloroethane in an oven-dried 2L three-necked flask equipped with a condenser and a nitrogen inlet under an argon atmosphere. The solution was refluxed for 2 days, then cooled to room temperature, concentrated to 1/4 of its volume under vacuum, and diluted with methanol (300 mL). The resulting precipitate was filtered off and washed with hot methanol to give the desired product as a green solid (1.33 g,72.7% yield). The compound was sublimated in 26% yield. Lambda (lambda) _max (DCM):668nm。

Example 2 Synthesis of exemplary Nuclear-disrupted photoactive Compounds containing imine-linked indandione groups

FIG. 35 provides an overview of an exemplary synthetic scheme that provides a synthetic route to a core-disrupted photoactive compound containing an imine-linked indandione group:

the synthesis of the compounds depicted in fig. 35 proceeds as follows:

compound XCVIII: to a 40mL scintillation vial connected to an adapter with a reflux condenser in a heated block was added ninhydrin (Compound XCVI, 1.44g, 0.00258 mol), hydroxylamine hydrochloride (0.60 g,0.00863 mol), deionized water (14 mL), and a magnetic coil. The reaction mixture was heated rapidly to 100 ℃ and refluxed under atmospheric conditions for 15 minutes. As the reaction proceeds, the solid dissolves and begins to form a yellow precipitate. Work-up was done by cooling to room temperature, filtration and washing with cold water to collect compound XCVIII in 90% (1.28 g).

Compound XCIX: to a 40mL scintillation vial with a magnetically coupled coil in a heated block was added compound XCVI (1.0 g,0.0571 mol) and acetic anhydride (1.5 mL). The mixture was heated to reflux, 140 ℃, and the mixture began to melt completely together and mix at 70 ℃. The reaction was refluxed for 25 minutes and then cooled rapidly to room temperature. The product in the bottle was precipitated using an ice bath, then washed with diethyl ether (10 ml,4×) and petroleum ether to give compound XCIX in 93.0% yield (1.1532 g).

Compound C: to a dry three-necked flask with an internal thermocouple under nitrogen protection were added a magnetic coupling screw, compound XLII (0.158 g,0.000276 mol), compound XCIX (0.1 g,0.00046 mol), cuTC (0.035 g,0.000184 mol) and anhydrous THF (15 mL). The mixture was sonicated to help dissolve the CuTC and then mixed at room temperature for 16 hours. The solution was concentrated in vacuo and then washed 3 times with hot isopropanol and then 2 times with cold dichloromethane to give compound C in 21.1% yield.

EXAMPLE 3 optical Properties of imine-linked photoactive Compounds

Compounds XIII and C were synthesized according to the schemes described in examples 1 and 2 herein to evaluate the difference in optical properties between photoactive compounds with olefinic linkers and photoactive compounds with core-disrupted analogs with imine linkers:

The compounds were dissolved into about 1 micromolar solutions and their ultraviolet-visible (UV-vis) absorption spectra were obtained. FIG. 36 provides a normalized UV-vis absorbance spectra showing peak absorbance of an olefin-linked compound at about 590nm and peak absorbance of an imine-linked compound at about 670 nm.

EXAMPLE 4 sublimation of photoactive Compounds containing Nuclear destruction and indandione

Several photoactive compounds were synthesized according to the protocol described in example 1 above to evaluate the difference in sublimation properties between photoactive compounds containing a nuclear-disrupted donor moiety and photoactive compounds containing a non-disrupted donor moiety, as well as between photoactive compounds containing an indandione moiety and photoactive compounds containing a dicyan methylene indanone moiety. The following nuclear-disrupted dicyan methyleneindanone-based compounds were synthesized: compound V and compound IX. The following undamaged dicyan methyleneindanone-based compounds were also synthesized: compound XXIX and compound XXX. The following nuclear-disrupted indandione compounds were also synthesized: compound XIII and compound XVII. The following uncorrupted indandione compounds were also synthesized: compound XXXII.

The purification of the synthesized photoactive compounds by vacuum sublimation, the results are summarized in fig. 37, and fig. 37 shows a graph of maximum sublimation yield of each compound as a function of molecular weight. Compound XI had a maximum sublimation yield of 13.5%, compound IX had a maximum sublimation yield of 46.3%, compound XXIX had a maximum sublimation yield of 0%, compound XXX had a maximum sublimation yield of 0%, compound XIII had a maximum sublimation yield of 85.7%, compound XVII had a maximum sublimation yield of 91.3%, and compound XXXII had a maximum sublimation yield of 31.1%.

Sublimation yields of the undamaged photoactive compound (open dots on fig. 37) and the core-damaged photoactive compound (solid dots on fig. 37%) were compared to observe the effect of core damage at the electron donor moiety. The change from the undamaged photoactive compounds XXIX, XXX and XXXII to the corresponding core-destroyed photoactive compounds XI, IX and XIII showed an increase in sublimation yield of 13.5%, 46.3% and 54.6%, respectively. These results indicate that the use of nuclear destruction in the electron donor moiety can be a suitable technique to achieve high volatility and be compatible with physical vapor deposition.

Sublimation yields of the photo-active compounds of the dicyandiamide indanone group (rounded points on fig. 37) and the photo-active compounds of the indandione group (diamond points on fig. 37%) were compared to observe the effect of the change in electron acceptor moiety from dicyandiamide indanone to indandione. The change from the dicyan methyleneindanone-based compounds XI, IX and XXIX to the corresponding indandione-based compounds XIII, XVII and XXXII showed an increase in sublimation yield of 72.2%, 45% and 31.1%, respectively. These results indicate that the use of indandione in the electron acceptor moiety can be a suitable technique to achieve high volatility and be compatible with physical vapor deposition.

Example 5-transparent photovoltaic device comprising photoactive Compounds containing Nuclear destruction and indandione

Fig. 38 illustrates the absorption coefficients of exemplary active layer materials that may be used in the various embodiments described herein. The absorption coefficient was determined by films of compounds IX, XIII, XVII and LXXV deposited by vacuum thermal evaporation. As shown in fig. 38, the active layer material is characterized by strong absorption peaks in the red region to the NIR region of the solar spectrum. These strong optical transitions at long wavelengths confirm that the molecular structure is preserved by a vacuum thermal evaporation process in which similar molecules without nuclear destruction or indandione units may decompose. Although the spectra of specific exemplary compounds are shown in fig. 38, examples are not limited to specific exemplary compounds, and other photoactive compounds may be used in various examples and embodiments.

Fig. 39A-D illustrate transparent photovoltaic device structures 3900-3903 according to several embodiments. The device structures 3900-3903 include a Bulk Heterojunction (BHJ) or Planar Mixed Heterojunction (PMHJ) active layer between a top electrode and a bottom electrode that contains a core-destroying compound or molecule as an active material that can be formed on a substrate by vacuum thermal evaporation, as described herein. In some embodiments, the core-disrupted molecule further comprises an indandione acceptor group. The ITO layer may correspond to an anode. MoO (MoO) ₃ The layer can be used asAs a hole injection layer and may be considered as part of the anode structure or as a buffer layer coupled to the anode. The P-hexaphenyl (P-6P) layer may be considered a buffer layer coupled to the anode. The Ag layer may correspond to a cathode. TPBi: C ₆₀ The layer may be considered to be part of the cathode structure or as a buffer layer coupled to the cathode. The TPBi layer may correspond to an optical layer or an encapsulation layer as a cathode. Although a particular exemplary electron donor (or acceptor) is shown in fig. 39, this configuration is not limiting and other donors and/or acceptors may be used in accordance with various embodiments.

Fig. 39A illustrates a transparent photovoltaic device structure 3900 according to one embodiment. The device structure 3900 includes a binary BHJ active layer between a top electrode and a bottom electrode, comprising cloalpc as an electron donor and a nuclear destruction molecule compound IX as an electron acceptor, the active layer being formed by vacuum thermal evaporation. In some embodiments, the ClAlPc to IX blend is maintained at a donor to acceptor ratio of 50:50.

Fig. 39B illustrates a transparent photovoltaic device structure 3901 according to one embodiment. The device structure 3901 includes a ternary BHJ active layer between a top electrode and a bottom electrode comprising TAPC and a nuclear-disrupted indandione-containing compound XIII as an electron donor, and fullerene C ₆₀ As an electron acceptor, the active layer is formed by vacuum thermal evaporation. In some embodiments, TAPC: XIII: C ₆₀ The blend was maintained at a donor to acceptor ratio of 10:10:80.

Fig. 39C illustrates a transparent photovoltaic device structure 3902 according to one embodiment. The device structure 3902 includes a PMHJ active layer between a top electrode and a bottom electrode, comprising SubNc as an electron donor, and a nuclear-disrupted and indandione-containing compound XVII as an electron acceptor, formed by vacuum thermal evaporation. In some embodiments, the subNc:XVII blend is maintained at a donor to acceptor ratio of 50:50, and a thin layer of subNc and XVII is coupled to the blend layer.

Fig. 39D illustrates a transparent photovoltaic device structure 3903 according to one embodiment. Device structure 3903 includes two electrodes between a top electrode and a bottom electrodeA meta-BHJ active layer containing indandione-containing compound LXXV as an electron donor, and fullerene C ₇₀ As an electron acceptor, the active layer is formed by vacuum thermal evaporation. In some embodiments LXXV: C ₇₀ The blend was maintained at a donor to acceptor ratio of 30:70.

Fig. 40A-C show current density versus voltage curves (fig. 40A), external Quantum Efficiency (EQE) curves (fig. 40B), and transmission spectra (fig. 40C) for the device structures shown in fig. 39A-39D. Specifically, the solid line corresponds to the device structure 3900, the broken line corresponds to the device structure 3901, the dot-dash line corresponds to the device structure 3902, and the dot-dashed line corresponds to the device structure 3903. As shown in fig. 40A, all devices exhibited strong rectification in terms of forward bias and photocurrent as well as power generation under 1-solar illumination (am1.5g spectrum) conditions. Based on the EQE spectra in fig. 40B and their corresponding absorption coefficients in fig. 38, it was confirmed that photocurrent had a significant contribution from the active compounds IX, XIII, XVII and LXXV. In fig. 40C, the transparency of the photovoltaic device was confirmed by their transmission spectra.

Table 1 lists electrical and optical device performance data from the current density-voltage curves (FIG. 40A) and transmission spectra (FIG. 40C) for the device structures shown in FIGS. 39A-39D. Specifically, data for compound IX corresponds to device structure 3900, data for compound XIII corresponds to device structure 3901, data for compound XVII corresponds to device structure 3902, and data for compound LXXV corresponds to device structure 3903. The function of the core-destroying or indandione-containing molecules in the active layer (electron donor or electron acceptor), other active materials paired with them, and the device parameter short-circuit current density (J) are listed _sc ) Open circuit voltage (V) _oc ) Fill Factor (FF), power Conversion Efficiency (PCE), and average visible light transmittance (T) _vis ). It can be seen that all devices 3900-3903 exhibit a T greater than 50% _vis The value highlights the compatibility of the example molecule with transparent photovoltaics.

Compounds of formula (I)	Function of	Pairing	J _sc (mA cm ^-2 )	V _OC (V)	FF	PCE(％)	T _vis (％)
								IX	Receptor(s)	ClAlPc	1.79	0.50	0.36	0.32	65.9
XIII	Donor(s)	TAPC，C ₆₀	3.33	0.87	0.54	1.57	68.4
								XVII	Receptor(s)	SubNc	2.68	0.76	0.48	0.99	57.3
LXXV	Donor(s)	C ₇₀	4.74	0.85	0.63	2.57	67.9

TABLE 1 summary of device Performance

Statement regarding incorporation by reference and alteration

All references in this disclosure, such as patent documents, include: issued or granted patents or equivalents; patent application publications; and non-patent documents or other source materials, the entire contents of which are incorporated herein by reference as if individually incorporated.

All patents and publications mentioned in the disclosure are indicative of the levels of skill of those skilled in the art to which the invention pertains. The references cited herein are incorporated by reference in their entirety to indicate the state of the art in some cases by the date of their filing and it is intended that this information may be used herein if desired to exclude (e.g., forego) certain implementations in the prior art. For example, when a compound is claimed, it is to be understood that compounds known in the art, including certain compounds disclosed in the references disclosed herein (particularly the referenced patent documents), are not intended to be included in the claims.

When a set of substituents is disclosed herein, it is to be understood that all individual members of these groups are disclosed separately, as well as all subgroups and classes that can be formed using the substituents. When markush groups or other groupings are used herein, all individual members of the group, as well as all combinations and subcombinations possible of the group, are intended to be individually included in the present disclosure. As used herein, "and/or" means that one, all, or any combination of items in a list that are separated by "and/or" are included in the list; for example, "1, 2, and/or 3" is equivalent to "1" or "2" or "3", or "1 and 2", or "1 and 3", or "2 and 3", or "1, 2, and 3".

Unless otherwise indicated, each of the formulations or combinations of components described or exemplified may be used in the practice of the invention. The specific names of materials are intended to be exemplary, as it is known to those skilled in the art that the same materials may be named differently. It is to be understood that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified may be employed in the practice of the invention without undue experimentation. All prior art known functional equivalents of any such methods, device elements, starting materials, and synthetic methods are intended to be included in this disclosure. Whenever a range is given in the specification, e.g., a temperature range, a time range, or a compositional range, all intermediate ranges and subranges, and all individual values included in the given range are intended to be included in the present disclosure.

As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended, and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of … …" excludes any element, step or ingredient not specified in the claim elements. As used herein, "consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claims. Any recitation of the term "comprising" herein, particularly in the description of components of a composition or in the description of elements of a device, is to be understood to include those compositions and methods consisting essentially of and consisting of the recited components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein.

Abbreviations that may be used in this specification include:

P-6P: 1-phenyl-4- [4- [4- (4-phenylphenyl) phenyl ] benzene

TPBi:2,2',2"- (1, 3, 5-benzenetriyl) -tris (1-phenyl-1-H-benzimidazole)

(2,2′,2"-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole))

ClAlPc: chloro (29H, 31H-phthalocyanine) aluminum

SubNc: chloro (subphthalocyanine) boron

TAPC:4,4' -cyclohexylidenebis [ N, N-bis (4-methylphenyl) aniline ]

The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Therefore, it should be understood that while the present invention has been specifically disclosed by preferred embodiments and implementations and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this disclosure as defined by the appended claims.

Claims

1. A photoactive compound having the formula:

A–D–A，

A-pi-D-A, or

A–pi–D–pi–A,

Wherein a is an electron acceptor moiety, wherein pi is a pi-bridging moiety, wherein D is an electron donor moiety comprising a central core and one or more planarity-disrupting moieties Z attached to the central core, wherein the central core has a planar structure, and wherein the one or more planarity-disrupting moieties Z are conformationally locked in a configuration out of the plane of the central core.

2. The photoactive compound of claim 1, having a molecular weight of 250 atomic mass units to 1200 atomic mass units.

3. The photoactive compound according to claim 1, characterized in that it exhibits a sublimation purification yield of 20% by mass or more.

4. The photoactive compound of claim 1, having a thermal decomposition temperature of 200 ℃ to 500 ℃.

5. The photoactive compound of claim 1, exhibiting a band gap of 0.5eV to 4.0 eV.

6. The photoactive compound of claim 1, at 0.2Torr to 10 ^-7 The sublimation temperature of 150 ℃ to 450 ℃ is exhibited under the pressure of Torr.

7. The photoactive compound of claim 1, wherein the central core comprises an aromatic, heteroaromatic, polycyclic aromatic, or polycyclic heteroaromatic moiety comprising one or more five-membered rings, one or more six-membered rings, or a combination of one or more five-membered rings and one or more six-membered rings.

8. The photoactive compound of claim 1, wherein the central core comprises one or more quaternary carbons.

9. The photoactive compound of claim 1, wherein D comprises or has the formula:

Wherein Z is a planarity disrupting moiety, wherein each X is independently O, S, se, NH, NR ^N 、CH ₂ 、C(R ^N ) ₂ 、Si(R ^N ) ₂ Or Ge (R) ^N ) ₂ Wherein R is ^N Is a branched, cyclic or linear alkyl or ester group having a molecular weight of 15amu to 100amu, wherein Y ³ Independently O or S, wherein Q is a quaternary center, and wherein Y ⁴ Independently CH, N or CR ^N 。

10. The photoactive compound according to claim 1,

wherein at least one planarity disrupting moiety Z is bonded to the quaternary center Q of the central core; or alternatively

Wherein D comprisesWherein Q is a quaternary center.

11. The photoactive compound of claim 10, wherein D comprises one or more of the following groups or heterocyclic analogues thereof:

each of which is unsubstituted or substituted with one or more methyl, ethyl or fluoro, or trifluoromethyl groups.

12. The photoactive compound according to claim 1,

wherein each Z is independently unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted cycloalkyl, unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted cycloalkenyl, unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted cyclopentadienyl, or unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted phenyl; or alternatively

Wherein two Z together form an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cycloalkyl, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cycloalkenyl, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cyclopentadienyl, or an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted phenyl; or alternatively

Wherein two Z together form a group comprising: an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused five-membered ring, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused six-membered ring, or an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused five-and six-membered ring; or alternatively

Wherein two Z's together form a heterocyclic group or a fused heterocyclic group.

13. The photoactive compound of claim 1, wherein each a independently comprises:

wherein each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, wherein each Y ¹ Independently C (CN) ₂ O, S or cyanoimines, wherein each Y ² Is CH or N or Y ² In the absence, A is linked to the D or pi moiety by a double bond, where each X ¹ Is independently O, S, se or NR ^O Wherein each R is ³ Is CN or C (CN) ₂ And wherein R is ^O Is a branched or straight chain alkyl group having a molecular weight of 15amu to 100 amu.

14. The photoactive compound of claim 1, wherein at least one a comprises indanone, indandione, indanthione, indandithione, dicyanomethyleneindanone, bis (dicyanomethylene) indane, or aryl-substituted indanone, indandione, indanthione, indandithione, dicyanomethyleneindanone, or bis (dicyanomethylene) indane.

15. The photoactive compound of claim 1, wherein at least one a comprises an imine bond connecting the electron acceptor moiety to the electron donor moiety or the pi-bridging moiety.

16. The photoactive compound of claim 1, wherein each pi independently comprises:

wherein each X ¹ Is independently O, S, se or NR ^N Wherein each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, wherein each X ² O, S, se, NH, NR independently ^N 、CH ₂ Or C (R) ^N ) ₂ Wherein each W is independently H, F, or branched or straight chain C1-C8 alkyl or branched or straight chain C1-C8 alkoxy, and wherein each R ^N Independently a branched, cyclic or linear alkyl or ester group having a molecular weight of 15amu to 100 amu.

17. The photoactive compound of claim 1, having the formula:

18. a photovoltaic device, comprising:

a substrate;

a first electrode coupled to the substrate;

a second electrode over the first electrode;

a first photoactive layer between the first electrode and the second electrode, wherein the first photoactive layer comprises the photoactive compound of claim 1; and

a second photoactive layer between the first electrode and the second electrode, wherein the second photoactive layer comprises a corresponding electron donor material or a corresponding electron acceptor material, and wherein the first photoactive layer and the second photoactive layer correspond to separate photoactive layers, partially mixed photoactive layers, or fully mixed photoactive layers.

19. The photovoltaic device of claim 18, wherein one or more or all of the substrate, the first electrode, the second electrode, the first photoactive layer, or the second photoactive layer is visible light transparent.

20. The photovoltaic device of claim 18, wherein one or more of the substrate, the first electrode, the second electrode, the first photoactive layer, or the second photoactive layer is partially transparent or opaque.

21. The photovoltaic device of claim 18, wherein the photoactive compound of claim 1 is an electron acceptor compound and wherein the second photoactive layer comprises a corresponding electron donor material.

22. The photovoltaic device of claim 18, wherein the photoactive compound of claim 1 is an electron donor compound and wherein the second photoactive layer comprises a corresponding electron acceptor material.

23. A method of manufacturing a photovoltaic device, the method comprising:

providing a substrate;

providing a first electrode coupled to the substrate;

depositing a photoactive layer comprising the photoactive compound of claim 1 on a visible light transparent electrode and a visible light transparent substrate by vapor deposition techniques; and

A second electrode is provided over the photoactive layer.

24. The method of claim 23, wherein depositing the photoactive layer comprises depositing the photoactive layer using a thermal evaporation process.

25. The method of claim 23, wherein one or more or all of the substrate, the first electrode, the second electrode, or the photoactive layer is visible light transparent.

26. The method of claim 23, wherein one or more of the substrate, the first electrode, the second electrode, or the photoactive layer is partially transparent or opaque.

27. A photoactive compound having the formula:

A–D–A，

A-pi-D-A, or

A–pi–D–pi–A,

Wherein a is an electron acceptor moiety, wherein pi is a pi-bridging moiety, wherein D is an electron donor moiety, and wherein at least one a comprises indandione, indanthione, indandithione, or aryl substituted indandione, indanthione, indandithione.

28. The photoactive compound of claim 27, having a molecular weight of 250 to 1200 atomic mass units.

29. The photoactive compound of claim 27, which exhibits a sublimation purification yield of greater than 20% by mass.

30. The photoactive compound of claim 27, having a thermal decomposition temperature of 200 ℃ to 500 ℃.

31. The photoactive compound of claim 27, exhibiting a band gap of 0.5eV to 4.0 eV.

32. The photoactive compound of claim 27, at 0.2Torr to 10 ^-7 The sublimation temperature of 150 ℃ to 450 ℃ is exhibited under the pressure of Torr.

33. The photoactive compound of claim 27, wherein at least one a comprises:

wherein each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, wherein each Y ¹ Is independently O or S, wherein Y ² Is CH or N or Y ² Absence of at least one ofEach a is linked to the D or pi moiety by a double bond.

34. The photoactive compound of claim 33, wherein one a comprises an a' group selected from:

wherein each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, wherein each Y in the A' group ¹ Independently C (CN) ₂ O, S or cyanoimines, wherein each Y ² Is CH or N or Y ² Absent, the A' group is linked to the D or pi moiety by a double bond, wherein each X ¹ Is independently O, S, se or NR ^O Wherein each R is ³ Is CN or C (CN) ₂ And wherein R is ^O Is a branched or straight chain alkyl group having a molecular weight of 15amu to 100 amu.

35. The photoactive compound of claim 27, wherein at least one a comprises an imine bond connecting the electron acceptor moiety to the electron donor moiety or the pi-bridging moiety.

36. The photoactive compound of claim 27, wherein D comprises an aromatic, heteroaromatic, polycyclic aromatic, or polycyclic heteroaromatic moiety comprising one or more five-membered rings, one or more six-membered rings, or a combination of one or more five-membered rings and one or more six-membered rings.

37. The photoactive compound of claim 27, wherein D comprises or has the formula:

wherein each X is independently O, S, se, NH, NR ^N 、CH ₂ 、C(R ^N ) ₂ 、Si(R ^N ) ₂ Or Ge (R) ^N ) ₂ Wherein R is ^N Is a branched, cyclic or linear alkyl or ester group having a molecular weight of 15amu to 100amu, wherein Y ³ Independently O or S, wherein Q is a quaternary center, wherein Y ⁴ Independently CH, N or CR ^N And wherein

Each Z is independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cycloalkyl, unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cycloalkenyl, unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cyclopentadienyl, or unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted phenyl; or alternatively

Two Z together form an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cycloalkyl, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cycloalkenyl, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted cyclopentadienyl, or an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted phenyl; or alternatively

Together, two Z form a group containing: an unsubstituted or methyl or ethyl, fluoro or trifluoromethyl substituted fused five-membered ring, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused six-membered ring, or an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused five-and six-membered ring; or alternatively

Two Z's together form a heterocyclic or fused heterocyclic group.

38. The photoactive compound of claim 27, wherein D comprises a central core and one or more planarity disrupting moieties Z attached to the central core, wherein the central core has a planar structure, and wherein the one or more planarity disrupting moieties Z are conformationally locked in an out-of-plane configuration of the central core.

39. The photoactive compound of claim 27, wherein each pi independently comprises:

40. The photoactive compound of claim 27, having the formula:

/>

41. a photovoltaic device, comprising:

a substrate;

a first electrode coupled to the substrate;

a second electrode over the first electrode;

a first photoactive layer between the first electrode and the second electrode, wherein the first photoactive layer comprises the photoactive compound of claim 27; and

42. The photovoltaic device of claim 41, wherein one or more or all of the substrate, the first electrode, the second electrode, the first photoactive layer, or the second photoactive layer is visible light transparent.

43. The photovoltaic device of claim 41, wherein one or more of the substrate, the first electrode, the second electrode, the first photoactive layer, or the second photoactive layer is partially transparent or opaque.

44. The photovoltaic device of claim 41, wherein the photoactive compound of claim 27 is an electron acceptor compound and wherein the second photoactive layer comprises a corresponding electron donor material.

45. The photovoltaic device of claim 41, wherein the photoactive compound of claim 27 is an electron donor compound and wherein the second photoactive layer comprises a corresponding electron acceptor material.

46. A method of manufacturing a photovoltaic device, the method comprising:

providing a substrate;

providing a first electrode coupled to the substrate;

depositing a photoactive layer comprising the photoactive compound of claim 27 on a visible light transparent electrode and a visible light transparent substrate by vapor deposition techniques; and

A second electrode is provided over the photoactive layer.

47. The method of claim 46, wherein depositing the photoactive layer comprises depositing the photoactive layer using a thermal evaporation process.

48. The method of claim 46, wherein one or more or all of the substrate, the first electrode, the second electrode, or the photoactive layer is visible light transparent.

49. The method of claim 46, wherein one or more of the substrate, the first electrode, the second electrode, or the photoactive layer is partially transparent or opaque.

50. A photoactive compound having the formula:

A–D–A，

A–pi–D–A，

A–pi–D–pi–A，

A-D, or

A–pi–D，

Wherein a is an electron acceptor moiety, wherein pi is a pi-bridging moiety, wherein D is an electron donor moiety, and wherein at least one a comprises an imine bond connecting the electron acceptor moiety to the electron donor moiety or the pi-bridging moiety.

51. The photoactive compound of claim 50 having a molecular weight of 250 to 1200 atomic mass units.

52. The photoactive compound of claim 50, wherein the sublimation purification yield is 20% by mass or greater.

53. The photoactive compound of claim 50 having a thermal decomposition temperature of 200 ℃ to 500 ℃.

54. The photoactive compound of claim 50, which exhibits a band gap of 0.5eV to 4.0 eV.

55. The photoactive compound of claim 27, at 0.2Torr to 10 ^-7 The sublimation temperature of 150 ℃ to 450 ℃ is exhibited under the pressure of Torr.

56. The photoactive compound of claim 50 wherein at least one A comprisesWherein a' is an imine-linked electron acceptor moiety.

57. The photoactive compound of claim 56 wherein each A comprisesWherein a' is an imine-linked electron acceptor moiety.

58. The photoactive compound of claim 56 wherein A' comprises a heterocycle.

59. The photoactive compound of claim 56, wherein at least one A comprises an imine linked indandione, an imine linked dicyandiamide indanone, an imine linked bis (dicyandiamide) indane, or an imine linked dicyanoethylene.

60. The photoactive compound of claim 50, wherein at least one a comprises:

61. The photoactive compound of claim 50, comprising:

A”–D–A，

A”–pi–D–A，

A–pi–D–A”，

a "-pi-D-pi-A, or

A”–pi–D–pi–A，

Wherein A' is a carbon-linked electron acceptor moiety.

62. The photoactive compound of claim 50, wherein each pi independently comprises:

/>

63. The photoactive compound of claim 50, wherein D comprises an aromatic, heteroaromatic, polycyclic aromatic, or polycyclic heteroaromatic moiety comprising one or more five membered rings, one or more six membered rings, or a combination of one or more five membered rings and one or more six membered rings.

64. The photoactive compound of claim 50, wherein D comprises or has the formula:

/>

wherein each X is independently O, S, se, NH, NR ^N 、CH ₂ 、C(R ^N ) ₂ 、Si(R ^N ) ₂ Or Ge (R) ^N ) ₂ Wherein R is ^N Is a branched, cyclic or linear alkyl or ester group having a molecular weight of from 15amu to 100amu, wherein each W is independently H, F, or a branched or linear C1-C8 alkyl or a branched or linear C1-C8 alkoxy group, wherein each R is independently H, F, cl, br, I, CH ₃ 、CF ₃ Or CN, wherein Y ³ Independently O or S, wherein Q is a quaternary center, wherein Y ⁴ Independently CH, N or CR ^N And wherein

Each Z is independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted cycloalkyl, unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted cycloalkenyl, unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted cyclopentadienyl, or unsubstituted or methyl, ethyl, fluoro, or trifluoromethyl substituted phenyl; or alternatively

Two Z's together form a group containing an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused five-membered ring, an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused six-membered ring, or an unsubstituted or methyl, ethyl, fluoro or trifluoromethyl substituted fused five-and six-membered ring; or alternatively

Two Z's together form a heterocyclic or fused heterocyclic group.

65. The photoactive compound of claim 50, wherein D comprises a central core and one or more planarity-disrupting moieties Z attached to the central core, wherein the central core has a planar structure, and wherein the one or more planarity-disrupting moieties Z are conformationally locked in an out-of-plane configuration of the central core.

66. The photoactive compound of claim 50 having the formula:

/>

67. a photovoltaic device, comprising:

a substrate;

a first electrode coupled to the substrate;

a second electrode over the first electrode;

a first photoactive layer between the first electrode and the second electrode, wherein the first photoactive layer comprises the photoactive compound of claim 50; and

68. The photovoltaic device of claim 67, wherein one or more or all of said substrate, said first electrode, said second electrode, said first photoactive layer, or said second photoactive layer is visible light transparent.

69. The photovoltaic device of claim 67, wherein one or more of said substrate, said first electrode, said second electrode, said first photoactive layer, or said second photoactive layer is partially transparent or opaque.

70. The photovoltaic device of claim 67, wherein the photoactive compound of claim 50 is an electron acceptor compound and wherein said second photoactive layer comprises a corresponding electron donor material.

71. The photovoltaic device of claim 67, wherein the photoactive compound of claim 50 is an electron donor compound and wherein said second photoactive layer comprises a corresponding electron acceptor material.

72. A method of manufacturing a photovoltaic device, the method comprising:

providing a substrate;

providing a first electrode coupled to the substrate;

depositing a photoactive layer comprising the photoactive compound of claim 50 on a visible light transparent electrode and a visible light transparent substrate by vapor deposition techniques; and

A second electrode is provided over the photoactive layer.

73. The method of claim 72, wherein depositing the photoactive layer comprises depositing the photoactive layer using a thermal evaporation process.

74. The method of claim 72, wherein one or more or all of the substrate, the first electrode, the second electrode, or the photoactive layer is visible light transparent.

75. The method of claim 72, wherein one or more of the substrate, the first electrode, the second electrode, or the photoactive layer is partially transparent or opaque.