CN117143118A - Donor-acceptor-donor materials for optoelectronic applications - Google Patents

Donor-acceptor-donor materials for optoelectronic applications Download PDF

Info

Publication number
CN117143118A
CN117143118A CN202310641501.7A CN202310641501A CN117143118A CN 117143118 A CN117143118 A CN 117143118A CN 202310641501 A CN202310641501 A CN 202310641501A CN 117143118 A CN117143118 A CN 117143118A
Authority
CN
China
Prior art keywords
group
combinations
aryl
alkoxy
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310641501.7A
Other languages
Chinese (zh)
Inventor
S·K·坎达帕
C·多布森
M·E·汤普森
P·I·久罗维奇
李永玺
S·R·福里斯特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Michigan
University of Southern California USC
Original Assignee
University of Michigan
University of Southern California USC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US18/322,819 external-priority patent/US20230391798A1/en
Application filed by University of Michigan, University of Southern California USC filed Critical University of Michigan
Publication of CN117143118A publication Critical patent/CN117143118A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present application relates to donor-acceptor-donor type materials for optoelectronic applications. There is provided a compound of formula I. Also provided are compositions comprising these compoundsFormulation of the formulation. Optoelectronic devices utilizing these compounds are also provided.

Description

Donor-acceptor-donor materials for optoelectronic applications
Cross-reference to related applications
The present application claims priority from U.S. provisional application No. 63/347,681, filed on 1, 6, 2022, which is incorporated herein by reference in its entirety.
Background
Optoelectronic devices rely on the optical and electronic properties of materials to electronically generate or detect electromagnetic radiation or to generate electricity from ambient electromagnetic radiation. Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic photovoltaic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) may make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors.
Photosensitive optoelectronic devices convert electromagnetic radiation into electricity. Solar cells, also known as Photovoltaic (PV) devices or cells, are a class of photoactive photovoltaic devices that are specifically used to generate electricity. PV devices that can generate electrical energy from light sources other than sunlight can be used to drive electrical loads to provide, for example, lighting, heating, or power electronic circuits or devices such as calculators, radios, computers, or remote monitoring or communication equipment. These power generation applications may involve charging of a battery or other energy storage device so that operation may continue when direct illumination from the sun or other light source is unavailable or to balance the power output of the PV device as required by a particular application.
Conventionally, photosensitive optoelectronic devices are composed of a plurality of inorganic semiconductors such as crystalline silicon, polycrystalline silicon, and amorphous silicon, gallium arsenide, cadmium telluride, and the like.
Recent efforts have focused on using Organic Photovoltaic (OPV) cells to achieve acceptable photovoltaic conversion efficiencies at economic production costs. OPV provides a low cost, lightweight and mechanically flexible approach to solar energy conversion. Small molecule OPVs also have the advantage of using well defined materials of molecular structure and weight compared to polymers. This results in a reliable purification path and the ability to deposit multiple layers using highly controlled thermal deposition without fear of dissolving and thus damaging pre-deposited layers or subcells.
OPV has unique advantages in addition to pursuing high device efficiency, such as the use of translucent solar cells for photovoltaic building integration (building integrated photovoltaics, BIPV). In view of the large surface area of windows and facades in modern urban environments, it is becoming increasingly important to develop translucent solar cells with high efficiency and high transmittance. For highly transparent solar cells, visible light will propagate uninhibited to the eye and therefore cannot be absorbed. Selective collection of Near Infrared (NIR) radiation may avoid competition between efficiency and transmittance. However, the inadequacies of the high performance NIR absorbers in conventional fu-based OPVs prevent the realization of efficient and highly transparent (in the visible) devices. Until now, the semi-transparent OPV based on the fu-acceptor only showed a PCE of less than or equal to 4% and an average visible light transmission of 61%.
Disclosure of Invention
In one aspect, the invention relates to a compound of formula I:
wherein Don and Don' are each independently represented by formula a or formula B:
wherein, in formula a and formula B:
* Represents a bond to Acc;
# represents a bond to Z or Z';
each X is independently selected from the group consisting of: o, S, se, te, geRR ', CRR ', siRR ', and NR;
Each Y is independently selected from the group consisting of: n and CR ";
R 1 、R 2 r, R' and R "independently represent hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and any two adjacent substituents are optionally joined to form a ring;
acc is a divalent electron accepting group;
z and Z ' are each together a donor group D and D ' respectively or a acceptor group A and A ', respectively;
wherein each of Acc, Z and Z' may be further substituted with one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents are optionally joined to form a ring.
In another aspect, the present disclosure provides a formulation comprising a compound of formula I as described herein.
In another aspect, the present disclosure provides an optoelectronic device comprising a compound of formula I as described herein.
Drawings
FIG. 1 shows the Natural Transition Orbitals (NTO) of the BT-PCE-X-Y-structure.
FIG. 2 shows NTOs of other BT-PCE-X-Y structures.
FIG. 3 is a normalized absorbance versus wavelength plot for BT-PCE and comparative compounds BT-CIC and Y6.
FIG. 4 is an illustration of the electrochemical band gap of the compound BT-PCE of the present invention and of the comparative compounds BT-CIC and Y6.
Fig. 5 is a plot of absorbance versus emission spectrum for BT-PCE.
FIG. 6 is a schematic illustration of a support electrolyte (n-Bu) 4 N + PF 6 - Cyclic voltammograms of BT-PCE measured in DCM.
Fig. 7 depicts the photovoltaic performance of BT-PCE.
FIG. 8 depicts the chemical structure of the acceptor molecules selected for DFT calculation and the corresponding HOMO LUMO values.
FIG. 9 is a table of calculated NTOs for BT-H-thiadiazole and BT-H-Py.
Fig. 10 depicts the UV-Vis absorption spectrum of BT-thiadiazoles.
FIG. 11 is a schematic illustration of a support electrolyte (n-Bu) 4 N + PF 6 - Cyclic voltammograms of BT-thiadiazoles measured in DCM.
Fig. 12 shows the calculated ntu of the aza-fulvene structure.
Fig. 13 shows the ntu of other aza-fulvene structures.
FIG. 14 is a UV-Vis absorption curve for AzOHEX and AzOHEX.
FIG. 15 is a schematic illustration of a support electrolyte (n-Bu) 4 N + PF 6 - Cyclic voltammograms of Az-OMe measured in DCM.
FIG. 16 is a schematic illustration of a support electrolyte (n-Bu) 4 N + PF 6 - Cyclic voltammograms of Az-OHex measured in DCM of (a).
Detailed Description
The present disclosure relates in part to small molecules with donor-acceptor-donor (DAD) triads for organic photovoltaic devices (OPVs).
As used herein, the term "organic" includes polymeric materials as well as small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and may be substantial in nature. In some cases, the small molecule may include a repeating unit. For example, the use of long chain alkyl groups as substituents does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into polymers, for example as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core of a dendron, which consists of a series of chemical shells built on the core. The dendritic core may be a fluorescent or phosphorescent small molecule emitter. Dendrimers may be "small molecules" and all dendrimers currently used in the field of organic optoelectronic devices are considered small molecules.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed" over "a second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed over" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photosensitive" when it is believed that the ligand contributes directly to the photosensitive properties of the emissive material. When the ligand is not considered to contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary", but the ancillary ligand may alter the properties of the photosensitive ligand.
As used herein, the terms "electrode" and "contact" may refer to a layer that provides a medium to carry current to an external circuit or to provide a bias current or voltage to a device. For example, electrodes or contacts may provide an interface between an active region of an organic photosensitive optoelectronic device and wires, leads, traces, or other means for transporting charge carriers to or from an external circuit. Examples of electrodes include anodes and cathodes, which may be used in photosensitive optoelectronic devices.
As used herein, the term "transparent" may refer to a material that allows transmission of at least 50% of incident electromagnetic radiation having a relevant wavelength. In photosensitive optoelectronic devices, it may be desirable to allow a maximum amount of ambient electromagnetic radiation from outside the device to enter the light guide active interior region. That is, the electromagnetic radiation must reach the photoconductive layer, where it can be converted into electricity by absorption by the photoconductive layer. This generally requires that at least one of the electrical contacts or electrodes should minimize absorption and minimize reflection of incident electromagnetic radiation. In some cases, such contacts should be transparent or at least translucent. In one embodiment, the transparent material may form at least a portion of an electrical contact or electrode.
As used herein, the term "translucent" may refer to a material that allows some, but less than 50% transmission of ambient electromagnetic radiation having a relevant wavelength. In the case of transparent or translucent electrodes, the opposing electrode may be a reflective material such that light that has passed through the cell without being absorbed is reflected back through the cell.
As used and depicted herein, "layer" refers to a component or member of a device (e.g., an optoelectronic device) that is primarily defined by, for example, thickness relative to other adjacent layers, and extends outwardly in length and width. It should be understood that the term "layer" is not necessarily limited to a single layer or sheet of material. Furthermore, it should be understood that the surface of certain layers, including the interface of such layers with other materials or layers, may be imperfect, wherein the surface represents an interpenetrating, entangled, or coiled network with other materials or layers. Similarly, it should also be understood that the layers may be discontinuous such that the continuity of the layers along the length and width may be disturbed or otherwise interrupted by other layers or materials.
As used herein, "photoactive region" refers to a region of a device that absorbs electromagnetic radiation to generate excitons. Similarly, a layer is "photosensitive" if it absorbs electromagnetic radiation to generate excitons. Excitons may dissociate into electrons and holes to generate a current.
As used herein, the terms "donor" and "acceptor" refer to the relative positions of the highest occupied molecular orbital ("HOMO") and the lowest unoccupied molecular orbital ("LUMO") energy levels of two contacted but distinct organic materials. A material is an acceptor if the LUMO level of the material in contact with another material is low. Otherwise it is the donor. In the absence of an external bias, it is energetically favorable to move electrons at the donor-acceptor junction into the acceptor material and holes into the donor material.
As used herein, and as will be generally understood by those of skill in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work function is typically measured as a negative number relative to the vacuum level, this means that the smaller the negative number (more negative), the "higher" the work function. On a conventional energy level diagram with the vacuum energy level on top, a "higher" work function is illustrated as being farther from the vacuum energy level in the downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different rule than work function.
As used herein, the term "band gap" of a polymer (E g ) May refer to the energy difference between HOMO and LUMO. The bandgap is typically reported in electron volts (eV). The band gap can be measured by UV-vis spectroscopy or cyclic voltammetry. "Low band gap" polymer may refer to a polymer having a band gap below 2eV, for example, a polymer that absorbs light at wavelengths greater than 620 nm.
The term "excitation binding energy" (E) B ) Can be referred to as follows: e (E) B ＝(M + +M - ) - (m+m), where M + And M - The total energy of positively and negatively charged molecules, respectively; m and M are each the first singlet (S 1 ) And molecular energy in the ground state. The excitation binding energy of the acceptor or donor molecule affects the energy shift required for efficient exciton dissociation. In some examples, the escape rate of holes increases with increasing HOMO offset. Exciton binding energy E of acceptor molecule B The decrease in (c) results in an increase in the hole escape rate for the same HOMO offset between the donor and acceptor molecules.
As used herein, "energy conversion efficiency" (PCE) (η ρ ) Can be expressed as:
wherein V is OC Is the open circuit voltage, FF is the fill factor, J SC Is short-circuit current, and P O Is the input optical power.
As used herein, "spin coating" may refer to a process of solution depositing a layer or film of one material (i.e., coating material) on the surface of an adjacent substrate or material layer. The spin coating process may include applying a small amount of coating material to the center of the substrate, which rotates at a low speed or does not rotate at all. The substrate is then rotated at a high speed to spread the coating material by centrifugal force. Rotation continues while the fluid rotates from the edge of the substrate until the desired film thickness is reached. The applied solvent is typically volatile and simultaneously evaporates. Thus, the higher the angular velocity of rotation, the thinner the film. The thickness of the film also depends on the viscosity and concentration of the solution and solvent.
As used herein, and as will be generally understood by those of skill in the art, if a first energy level is closer to a vacuum energy level, then a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level. Since Ionization Potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an Electron Affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with vacuum energy level on top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears to be closer to the top of the figure than the "lower" HOMO or LUMO energy level.
As used herein, and as will be generally understood by those of skill in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work function is typically measured as a negative number with respect to vacuum level, this means that the smaller the negative number, the "higher" the work function. On a conventional energy level diagram with the vacuum energy level on top, a "higher" work function is illustrated as being farther from the vacuum energy level in the downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different rule than work function.
The terms "halo", "halogen" and "halide" may be used interchangeably and refer to fluorine, chlorine, bromine and iodine.
The term "pseudohalogen" refers to a polyatomic analog of halogen that is similar in chemical nature to true halogen, allowing it to replace halogen in several classes of compounds. Exemplary pseudohalogens include, but are not limited to, nitriles, cyanides, isocyanides, cyanate esters, isocyanates, thundertes, thiocyanates, isothiocyanates, selenocyanates, telluronates, azides, cobalt tetracarbonyl, trinitromethanes, and tricyanomethanate groups.
The term "acyl" refers to a substituted carbonyl (C (O) -R s )。
The term "ester" refers to a substituted oxycarbonyl (-O-C (O) -R) s or-C (O) -O-R s ) A group.
The term "ether" means-OR s A group.
The terms "thio" or "thioether" may be used interchangeably and refer to-SR s A group.
The term "sulfinyl" refers to-S (O) -R s A group.
The term "sulfonyl" refers to-SO 2 -R s A group.
The term "phosphino" refers to-P (R s ) 3 Groups, where each R s May be the same or different.
The term "silane group" means-Si (R s ) 3 Groups, where each R s May be the same or different.
The term "borane" refers to-B (R s ) 2 A group or Lewis addition product-B (R) s ) 3 A group, wherein R is s Can be the same orDifferent.
In each of the above substances, R s May be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s Selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferably, the alkyl group is an alkyl group having one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, and the like. Furthermore, alkyl groups are optionally substituted.
The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, and the like. Furthermore, cycloalkyl groups are optionally substituted.
The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, in which at least one carbon atom is replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. In addition, heteroalkyl or heterocycloalkyl groups are optionally substituted.
The term "alkenyl" refers to and includes both straight and branched alkenyl groups. Alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl is essentially cycloalkyl including at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Preferred alkenyl, cycloalkenyl or heteroalkenyl groups are those containing from two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl or heteroalkenyl groups are optionally substituted.
The term "alkynyl" refers to and includes both straight and branched chain alkynyl groups. Preferably, alkynyl is alkynyl containing from two to fifteen carbon atoms. In addition, alkynyl groups are optionally substituted.
The term "aralkyl" or "arylalkyl" is used interchangeably and refers to an alkyl group substituted with an aryl group. In addition, aralkyl groups are optionally substituted.
The term "heterocyclyl" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Heteroaromatic cyclic groups may be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, as well as cyclic ethers/thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be optionally substituted.
The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycyclic ring may have two or more rings shared by two adjacent rings (the rings being "fused") in which at least one ring is an aromatic hydrocarbon group, for example the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. Preferably, aryl is aryl containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Aryl groups having six carbons, ten carbons or twelve carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chicory, perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene and naphthalene. Furthermore, aryl groups are optionally substituted.
The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, si and Se. In many cases O, S or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The polycyclic heterocyclic ring system may have two or more rings shared by two adjacent rings (the rings being "fused") in which at least one ring is heteroaryl, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. The polycyclic heteroaromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferably heteroaryl is heteroaryl containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene pyridine, thienodipyridine, benzoselenophene pyridine and selenophene bipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-borazine, 1, 2-boron-nitrogen, 1-nitrogen-boron-nitrogen-1, 4-boron-nitrogen-boron-like compounds. Furthermore, heteroaryl groups are optionally substituted.
Of particular interest among the aryl and heteroaryl groups listed above are triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole groups, and their respective corresponding aza analogues.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl, and heteroaryl as used herein are independently unsubstituted or independently substituted with one or more common substituents.
In many cases, the universal substituent is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some cases, preferred universal substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.
In some cases, preferred universal substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, thio, and combinations thereof.
In other cases, more preferred universal substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms "substituted" and "substituted" refer to substituents other than H bonded to a relevant position, such as carbon or nitrogen. For example, when R 1 When monosubstituted, then one R 1 It must not be H (i.e., substitution). Similarly, when R 1 When two are substituted, two R 1 It must not be H. Similarly, when R 1 R represents no substitution 1 For example, it may be hydrogen of available valence of the ring atoms, such as carbon atoms of benzene and nitrogen atoms in pyrrole, or for ring atoms having a fully saturated valence, it may simply represent none, such as nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atom.
As used herein, "combination thereof" means that one or more members of the applicable list combine to form a known or chemically stable arrangement that one of ordinary skill in the art would contemplate from the applicable list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl may combine to form a halogenated alkyl substituent; and halogen, alkyl and aryl may be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In another instance, the term substitution includes a combination of two groups. Preferred combinations of substituents are substituents containing up to fifty atoms other than hydrogen or deuterium, or substituents comprising up to forty atoms other than hydrogen or deuterium, or substituents comprising up to thirty atoms other than hydrogen or deuterium. In many cases, a preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.
The term "aza" in the fragments described herein, i.e. azadibenzofuran, azadibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic ring may be replaced with a nitrogen atom, for example and without limitation, azatriphenylene encompasses dibenzo [ f, H ] quinoline and dibenzo [ f, H ] quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. patent application No. 8,557,400, patent publication No. WO 2006/095951, and U.S. patent application publication No. US 2011/0037057 (all of which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Reference is also made to color (Ming Yan) et al, "Tetrahedron", 2015,71,1425-30 and attlrodt (Atzrodt) et al, "International edition of applied chemistry (Angew. Chem. Int. Ed.)" (review) 2007,46,7744-65, which are incorporated herein by reference in their entirety, which describe the deuteration of methylene hydrogen in benzylamine and the efficient route to replacement of aromatic ring hydrogen with deuterium, respectively.
It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.
In some cases, a pair of adjacent substituents may optionally be joined or fused into a ring. Preferred rings are five-, six-or seven-membered carbocycles or heterocycles, including two cases: a portion of the ring formed by the substituent pairs is saturated and a portion of the ring formed by the substituent pairs is unsaturated. As used herein, "adjacent" means that the two substituents involved can be located adjacent to each other on the same ring, or on two adjacent rings having two closest substitution available positions, e.g., the 2,2' positions in biphenyl, or the 1, 8 positions in naphthalene, so long as they are capable of forming a stable fused ring system.
Any of the layers of the various embodiments may be deposited by any suitable method unless otherwise specified. Preferred methods for the organic layer include thermal evaporation, ink-jet (as described, for example, in U.S. patent nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety), organic vapor deposition (OVPD) (as described, for example, in U.S. patent No. 6,337,102, which is issued to forster et al, which is incorporated by reference in its entirety), and deposition by Organic Vapor Jet Printing (OVJP) (as described, for example, in U.S. patent No. 7,431,968, which is incorporated by reference in its entirety). Other suitable deposition methods include spin-coating and other solution-based processes. The solution-based process is preferably carried out under nitrogen or an inert atmosphere. For other layers, the preferred method includes thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. patent nos. 6,294,398 and 6,468,819, incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and Organic Vapor Jet Printing (OVJP). Other methods may also be used. The material to be deposited may be modified to be compatible with the particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 carbons or more may be used, and 3 to 20 carbons are a preferred range. A material with an asymmetric structure may have better solution processibility than a material with a symmetric structure because an asymmetric material may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices made in accordance with embodiments of the present invention may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from harmful substances exposed to the environment including moisture, vapors and/or gases, etc. The barrier layer may be deposited over the substrate, electrode, under the substrate, electrode, or beside the substrate, electrode, or on any other portion of the device, including the edge. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include a composition having a single phase and a composition having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. patent No. 7,968,146, PCT patent application No. PCT/US2007/023098, and PCT/US2009/042829, which are incorporated herein by reference in their entirety. To be considered as a "mixture", the aforementioned polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same reaction conditions and/or simultaneously. The weight ratio of polymeric material to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.
Devices made in accordance with embodiments of the present invention may be incorporated into a wide variety of electronic component modules (or units) that may be incorporated into a wide variety of electronic products or intermediate components.
The materials and structures described herein may be applied to devices other than organic solar cells. For example, other optoelectronic devices such as organic electroluminescent devices (OLEDs) and organic photodetectors may use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.
According to one aspect, the present disclosure relates to compounds of formula I:
wherein Don and Don' are each independently represented by formula a or formula B:
wherein, in formula a and formula B:
* Represents a bond to Acc;
# represents a bond to Z or Z';
each X is independently selected from the group consisting of: o, S, se, te, geRR ', CRR ', siRR ', and NR;
each Y is independently selected from the group consisting of: n and CR ";
R 1 、R 2 r, R' and R "independently represent hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and any two adjacent substituents are optionally joined to form a ring;
Acc is a divalent electron accepting group;
z and Z ' are each together a donor group D and D ' respectively or a acceptor group A and A ', respectively;
wherein each of Acc, Z and Z' may be further substituted with one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents are optionally joined to form a ring.
In one embodiment, acc is an electron accepting group selected from the group consisting of: SO (SO) 2 、CF 2 Imines, ketones, polycyclic aromatic compounds, polycyclic heteroaromatic compounds, alkyl borates, aryl borates, alkoxy borates, and combinations thereof.
In one embodiment, D and D' are independently selected from the group consisting of: alkoxy, aryloxy, heteroaryloxy, alkenyloxy, alkyloxy, allyloxy, amino, dialkylamino, diarylamino, sulfanyl, thiiranyl, and combinations thereof; and
In one embodiment, a and a' are independently selected from the group consisting of: halogen, NO 2 、CN、SO 2 R、CF 3 Imines, ketones, aldehydes, polycyclic aromatic compounds, polycyclic heteroaromatic compounds, alkyl borates, aryl borates, alkoxy borates, and combinations thereof; and
in one embodiment, each of Acc, Z, and Z' may be further substituted with one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring.
In one embodiment, the compound is represented by formula II:
wherein, in the formula II,
acc is a divalent electron accepting group selected from the group consisting of: polycyclic aromatic compounds, polycyclic heteroaromatic compounds, arylborates, alkoxyborates, and combinations thereof;
each X is independently selected from the group consisting of: o, S, se, te, geRR ', CRR ', siRR ', and NR;
Each Y is independently selected from the group consisting of: n and CR ";
z and Z ' are each together a donor group D and D ' respectively or a acceptor group A and A ', respectively;
d and D' are independently selected from the group consisting of: alkoxy, aryloxy, heteroaryloxy, alkenyloxy, alkyloxy, allyloxy, amino, dialkylamino, diarylamino, sulfanyl, thiiranyl, and combinations thereof;
a and a' are independently selected from the group consisting of: halogen, NO 2 、CN、SO 2 R、CF 3 Imines, ketones, aldehydes, polycyclic aromatic compounds, polycyclic heteroaromatic compounds, alkyl borates, aryl borates, alkoxy borates, and combinations thereof;
R 1 、R 1 '、R 2 、R 2 ', R, R ' and R ' independently represent hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
any two adjacent substituents are optionally joined to form a ring.
In one embodiment, R 1 And R is 2 Is represented by one of the following structures:
in one embodiment, acc is represented by one of the following structures:
/>
wherein wavy lines represent bonds to Don and Don';
wherein each X independently represents O, S, se, NR 5 Or C (CN) 2 ；
Wherein Y and Z independently represent CR 4 And N;
wherein the method comprises the steps ofRepresents an optional aryl, heteroaryl, polyaromatic or polyheteroaryl ring condensate;
wherein R is 3 、R 4 、R 5 And R is 6 Independently represents hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein each R is 7 Independently an electron withdrawing group selected from the group consisting of: halogen, haloalkyl, aryl, heteroaryl, nitrile, and combinations thereof; and
wherein any two adjacent substituents are optionally joined to form a ring.
In one embodiment, Z and Z' are independently represented by one of the following structures:
/>
wherein each X independently represents O, S, se, NR C Or C (CN) 2 ；
R A 、R B 、R C And R is D Independently represents hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents are optionally joined to form a ring.
In one embodiment, Z and Z' are each an acceptor group selected from the group consisting of:
in one embodiment, Z and Z' are each a donor group selected from the group consisting of:
in one embodiment, acc is selected from the group consisting of:
in one embodiment, the compound is represented by one of the following structures:
wherein, in formula C:
x is F, CF 3 、CN、SO 3 H or SO 2 Me; and
y is NH 2 、NMe 2 、NPh 2 、N(4-OMePh) 2 、N(3,4,5-(OMe)Ph) 2 Or N (2, 4,6- (OMe) Ph) 2 ；
/>
/>
/>
According to another aspect, a formulation comprising a compound described herein is also disclosed.
Organic photovoltaic cell
In one aspect, the invention relates to an OPV device comprising a compound of the present disclosure. In one embodiment, an OPV apparatus includes an anode; a cathode; and an active material disposed between the anode and the cathode, wherein the active material comprises an acceptor and a donor.
In one embodiment, the OPV device comprises a single junction organic photovoltaic device. In one embodiment, an OPV device comprises two electrodes having an anode and a cathode in a stacked relationship, at least one donor composition, and at least one acceptor composition, wherein a donor-acceptor material or active layer is disposed between the two electrodes. In one embodiment, one or more intermediate layers may be disposed between the anode and the active layer. Alternatively or additionally, one or more intermediate layers may be disposed between the active layer and the cathode.
In one embodiment, the anode comprises a conductive oxide, a thin metal layer, or a conductive polymer. In one embodiment, the anode comprises a conductive metal oxide. Exemplary conductive metal oxides include, but are not limited TO, indium Tin Oxide (ITO), tin Oxide (TO), gallium Indium Tin Oxide (GITO), zinc Oxide (ZO), and Zinc Indium Tin Oxide (ZITO). In one embodiment, the anode comprises a metal layer. Exemplary metals for the metal layer include, but are not limited to Ag, au, pd, pt, ti, V, zn, sn, al, co, ni, cu, cr and combinations thereof. In one embodiment, the metal layer comprises a thin metal layer. In one embodiment, anode 102 comprises a conductive polymer. Exemplary conductive polymers include, but are not limited to, polyaniline (PANI) or 3, 4-polyethylene dioxythiophene (PEDOT: PSS) polystyrene sulfonate. In one embodiment, the anode has a thickness between about 0.1nm and 100 nm. In one embodiment, the anode has a thickness between about 1-10 nm. In one embodiment, the anode has a thickness between about 0.1nm and about 10 nm. In one embodiment, the anode has a thickness between about 10-100 nm. In one embodiment, the anode comprises a transparent or translucent conductive material.
In one embodiment, the cathode comprises a conductive oxide, a metal layer, or a conductive polymer. Exemplary conductive oxides, metal layers, and conductive polymers are described elsewhere herein. In one embodiment, the cathode comprises a thin metal layer. In one embodiment, the cathode comprises a metal or metal alloy. In one embodiment, the cathode may comprise Ca, al, mg, ti, W, ag, au or another suitable metal or alloy thereof. In one embodiment, the thickness of the cathode is between about 0.1-100 nm. In one embodiment, the thickness of the cathode is between about 1-10 nm. In one embodiment, the thickness of the cathode is between about 0.1-10 nm. In one embodiment, the thickness of the cathode is between about 10-100 nm. In one embodiment, the cathode comprises a transparent or translucent conductive material.
In one embodiment, the OPV device may include one or more charge collection/transport interlayers disposed between the electrode and the active region or layer. In one embodiment, the OPV device includes one or more intermediate layers. In one embodiment, the intermediate layer comprises a metal oxide. Exemplary metal oxides include, but are not limited to, moO 3 、MoO x 、V 2 O 5 ZnO and TiO 2 . In one embodiment, the first intermediate layer has the same composition as the second intermediate layer. In one embodiment, the first intermediate layer and the second intermediate layer have different compositions. In one embodiment, the thickness of the intermediate layers is each independently between about 0.1-100 nm. In one embodiment, the thickness of the intermediate layers is each independently between about 1-10 nm. In one embodiment, the thickness of the intermediate layers is each independently between about 0.1-10 nm. In one embodiment, the thickness of the intermediate layers is each independently between about 10-100 nm.
In one embodiment, the device includes various layers of a tandem or multi-junction type photovoltaic device. In one embodiment, an OPV device includes two electrodes having anodes and 204 in a stacked relationship, at least one donor composition, and at least one acceptor composition disposed within a plurality of active layers or regions between the two electrodes. Other active layers or regions may also be present. In one embodiment, the anode and cathode each independently comprise a conductive oxide, a thin metal layer, or a conductive polymer. Exemplary conductive oxides, metal layers, and conductive polymers are described elsewhere herein.
In one embodiment, the OPV device includes one or more intermediate layers disposed between the anode and the first active layer. Alternatively or additionally, at least one intermediate layer may be disposed between the second active layer and the cathode. In one embodiment, the OPV device includes one or more intermediate layers disposed between the first active layer and the second active layer. In one embodiment, the OPV device includes a first intermediate layer. In one embodiment, the OPV device includes a second intermediate layer. In one embodiment, the OPV device includes a third intermediate layer. In one embodiment, the OPV device comprises first and second intermediate layers. In one embodiment, the OPV device comprises first and third intermediate layers. In one embodiment, the OPV device comprises a second and a third intermediate layer. In one embodiment, the OPV device comprises first, second and third intermediate layers. In one embodiment, the first, second and/or third intermediate layers comprise a metal oxide. Exemplary metal oxides are described elsewhere herein.
Experimental examples
Small molecules are more reliable materials for organic photovoltaic devices (OPVs) than polymers due to reproducible synthesis and ease of purification. Especially for device fabrication involving vapor deposition techniques, small molecules are obvious candidates compared to polymers.
Small molecules with an acceptor-donor-acceptor (ADA) type triad, where two acceptor molecules are covalently linked to either end of a donor molecule, are widely used in high efficiency OPV devices (with PCEs of about 17%). IT-IC, IT-4F, m-ITIC molecules are some of such ADA-type molecules in high efficiency devices, to name a few. On the other hand, OPV with donor-acceptor-donor (DAD) type molecules is relatively rarely studied. The current efficiency of OPV devices with DAD-type molecules is also relatively low compared to devices with ADA-type molecules. Here, we have attempted to develop novel DAD-type small molecules for semitransparent organic photovoltaic devices.
PCE-10 polymers, such as 1, are used in some highly efficient translucent OPV devices. It consists of monomer units having a Benzodithiophene (BDT) derivative linked to a thienothiophene unit. The compounds described herein relate to monomeric analogs of PCE-10 polymers. The monomeric analog can be represented by a simplified structure 2, which consists of a thienothiophene having BDT units attached to either side of the thiophene at positions 2 and 5 and is similar to a donor-acceptor-donor type moiety. To determine the optimal structure with NIR absorption, DFT/TD-DFT calculations were performed for structure 2 with different functional groups X and Y (table 1, fig. 1 and fig. 2). In structure 2, X and Y represent groups having electron donating and electron withdrawing properties, respectively, for maintaining donor-acceptor-donor (DAD) characteristics. The DFT/TD-DFT calculation helps to optimize the synthesis of the feasible structure, identifying fluorine as the pull electronics unit X and bis (4-methoxy) diphenylamine group as the electron donating unit Y being the most advantageous group.
Table 1: DFT/TD-DFT calculation of BT-PCE-X-Y-structure and CV data of BT-PCE
The calculation and experimental data in table 1, fig. 1 and fig. 2 support the following structures as donor materials for organic photovoltaic devices. And synthesizing the BT-PCE (3) and obtaining the photophysical data thereof. BT-PCE exhibits UV-Vis absorbance with a very large absorbance at 550nm, tailing around 750nm (fig. 3), and an optical bandgap of 2.02eV and an electrochemical bandgap of 2.28eV (fig. 4). The UV-Vis absorption and emission spectra of BT-PCT are provided in FIG. 5. A Cyclic Voltammogram (CV) of BT-PCE is provided in fig. 6. In device fabrication with BT-PCE donors and Y6 acceptors, it was shown that the energy conversion efficiency (PCE) was 1.52% (fig. 7).
BT-PCE was synthesized using a commercially available thienothiophene acceptor unit, 2-ethylhexyl 4, 6-dibromo-3-fluorothieno [3,4-b ] thiophene-2-carboxylate, which was then subjected to a Stille coupling (Stille coupling) with a benzodithiophene trimethylstannyl derivative.
To further increase the diversity of DAD molecules for semitransparent OPVs with better energy conversion efficiency, the central acceptor unit of BT-PCE was modified. The following moieties 4a-4g were selected for DFT calculations to screen the structure for the acceptor unit with the aim of identifying the acceptor with the lowest LUMO energy level. DFT calculations indicated that benzothiadiazole 4e and 9, 10-phenanthrenequinone thienopyrazine 4f are better receptors with lowest LUMO energies of-2.34 eV and-2.50 eV, respectively (Table 2).
Table 2: the chemical structure of the receptor molecule selected for DFT calculation and the corresponding HOMO LUMO value.
Similarly, DFT calculations of the donor component (fig. 8) reveal that BDT unit 7b has the highest HOMO level (-4.65 eV) as the donor molecule.
Based on these DFT calculations, DAD type molecules are synthesized in which donor unit 7b is tethered to acceptor cores 4e and 4f. The DFT/TDDFT calculations are performed separately for these systems. And synthesizing BT-thiadiazole 9 and BT-Py 11. HOMO/LUMO values were calculated by DFT calculation and electrochemical method (table 3, table 4 and fig. 9). The UV-Vis absorption spectrum of BT-thiadiazole is shown in FIG. 10. The CV of BT-thiadiazole is shown in FIG. 11.
Table 3: the chemical structures of BT-thiadiazoles and BT-H-thiadiazoles, and the DFT/TD-DFT calculation and CV data of BT-thiadiazoles.
Table 4: BT-Py, BT-H-Py chemical structure and DFT/TD-DFT calculation, CV data of BT-Py.
The aza-fulvene type DAD structure with a central aza-fulvene core was also examined. Calculated data based on these compounds are presented in table 5. The natural transition orbitals of the azafulvene structure are shown in fig. 12 and 13. UV-Vis absorption spectra of Az-H, az-OMe and AzOHEX are presented in FIG. 14. The CV of Az-OMe is presented in FIG. 15. The CV of Az-OHEX is presented in FIG. 16.
Table 5: the lowest energy vertical transition of the aza-fulvene structure results from the HOMO/LUMO energy of the calculated and CV data.
Detailed description of the synthesis
Synthesis and characterization data of BT-PCE
Scheme 1: general scheme for synthesizing BT-PCE 15.
Synthesis of benzodithiophene-4, 8-bis (triflate) 2
To a suspension of benzodithiophene-4, 8-dione 1 (1.2 g,5.45mmol,1 eq.) in 15mL ethanol was added sodium borohydride (457 mg,12.0mmol,2.2 eq.). It was refluxed under nitrogen for 20 hours. After cooling to room temperature, the reaction mixture was poured into 10ml of 1n HCl. The green precipitate of benzodithiophene-4, 8-diol was washed several times with deionized water and dried under high vacuum at 70 ℃ for 3 hours.
The crude material (1.1 g,4.9mmol,1 eq.) was used as such in the next step. It was placed in a dry round bottom flask and 35mL of dichloromethane was added under nitrogen. Then, anhydrous pyridine (1.3 mL,14.7mmol,3 eq.) was added and cooled to 0deg.C. After dropwise addition of trifluoromethanesulfonic anhydride (2.7 mL,14.7mmol,3 eq.) the reaction mixture was stirred at 0deg.C for 12 hours. After 12 hours, the reaction mixture was warmed to room temperature. Water and 1N HCl were added. The organic layer was separated. The aqueous layer was extracted with dichloromethane (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 1.4g of product (isolated yield=63%).
1 H-NMR(400MHz,CDCl 3 ,δ)7.67(dd,J＝5.6,0.5Hz,2H),7.56(d,J＝5.6Hz,2H)。
13 C NMR(101MHz,CDCl 3 ,δ)135.70,132.95,132.53,130.39,123.35,120.16,119.51,116.97,113.78。
Synthesis of 4, 8-diphenyl benzodithiophene 3
Trifluoromethanesulfonate 2 (1.4 g,2.9mmol,1 eq.) is placed in a round bottom flask and phenylboronic acid (1.04 g,8.3mmol,3 eq.) tetrakis (triphenylphosphine) palladium [0] (99 mg,0.0856mmol,0.05 eq.) is added. Next, 75mL of a pre-deaerated solution of anhydrous tetrahydrofuran and 1M aqueous sodium carbonate was added. The reaction mixture was stirred at reflux for 16 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature and quenched by addition of deionized water. Ethyl acetate (50 mL) was added and the organic layer was separated. The aqueous layer was extracted with ethyl acetate (30 mL. Times.3). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 810mg of product (isolated yield = 82%).
1 H-NMR(400MHz,CDCl 3 ,δ)7.75-7.68(m,4H),7.60-7.55(m,4H),7.53-7.47(m,2H),7.40(d,J＝5.7Hz,2H),7.34(s,2H)。
Synthesis of 2-bromo-4, 8-diphenyl benzodithiophene 4
4, 8-diphenylbenzodithiophene 3 (1 g,3.1mmol,1 eq.) was placed in a round bottom flask. N-bromosuccinimide (552 mg,3.1mmol,1 eq.) was added. Next, 50mL of chloroform was added under nitrogen. Then 8mL of glacial acetic acid was slowly added at room temperature. The reaction mixture was stirred at room temperature overnight. The reaction was then subjected to thin layer chromatography. After stirring for 12 hours, the reaction mixture was quenched by the addition of deionized water. The organic layer was separated. The aqueous layer was extracted with dichloromethane (3X 10 mL). The combined organic layers were washed with saturated sodium carbonate solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 555mg of product (isolated yield = 46%). Unreacted 4, 8-diphenylbenzodithiophene (272 mg) was recovered. Small amounts of dibromo product are also formed.
1 H-NMR(400MHz,CDCl 3 ,δ)δ7.67(ddd,J＝8.1,2.3,1.3Hz,4H),7.60-7.54(m,4H),7.53-7.47(m,2H),7.43(d,J＝5.7Hz,1H),7.33-7.28(m,2H)。
13 C NMR(101MHz,CDCl 3 ,δ)139.03,138.78,138.71,138.48,136.00,135.65,129.72,129.67,129.26,129.13,128.99,128.96,128.45,128.41,127.60,125.61,122.88,116.12。
Synthesis of 2- (N, N-diphenylamine) -4, 8-diphenylbenzodithiophene 6
2-bromo-4, 8-diphenylbenzodithiophene 4 (555 mg,1.31mmol,1 eq.) was placed in a round bottom flask. N, N-4-methoxydiphenylamine (308 mg,1.34mmol,1.02 eq), tris (dibenzylideneacetone) dipalladium [0] (24 mg,0.02mmol,0.015 eq.), tris-tert-butylphosphine (0.2 mL of 10% W/W solution, 0.06mmol,0.046 eq.) and sodium tert-butoxide (132 mg,1.37mmol,1.04 eq.) were added. Then 50mL of anhydrous toluene was added. The reaction mixture was stirred at reflux for 24 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature and deionized water was added. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 519mg of product (isolated yield = 69%).
1 H-NMR(400MHz,CDCl 3 ,δ)7.67-7.61(m,4H),7.49(tdd,J＝8.1,7.4,2.9,1.8Hz,4H),7.44-7.37(m,2H),7.25-7.19(m,2H),7.15-7.10(m,4H),6.82-6.76(m,4H),6.54(s,1H),3.77(s,6H)。
Synthesis of trimethyltin derivative 7
2- (N, N-Diphenylamine) -4, 8-diphenylbenzodithiophene 7 (430 mg,0.7547mmol,1.0 eq.) was placed in a dry round bottom flask. 25mL of anhydrous THF was added. The reaction mixture was cooled to-78 ℃. Next, n-BuLi (2.5M, 0.326mL,0.839mmol,1.1 eq.) was slowly added and stirred at the same temperature for 2 hours. After 2 hours, the reaction mixture was warmed to 0 ℃ and stirred for 15 minutes. Then, it was further cooled to-78 ℃. Trimethyltin chloride (1M, 1mL,1.0mmol,1.3 eq.) was added. It was stirred at the same temperature for 4 hours. Then, the temperature was slowly warmed to room temperature and stirred at room temperature for another 12 hours. Then, quench by adding water and add 10mL ethyl acetate. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 10 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure to give 516mg of material. It was used as such in the next step without further purification. The product was confirmed by NMR of the crude material.
Synthesis of BT-PCE 9
Trimethyltin derivative 7 was placed in a round bottom flask (500 mg,0.557mmol,2.0 eq). 2-ethylhexyl-4, 6-dibromo-3-fluorothieno [3,4-b ] thiophene-2-carboxylate 8 (100 mg,0.2785mmol,1.0 eq.) and tetrakis (triphenylphosphine) palladium [0] (30 mg,0.0259mmol,0.01 eq.) were added. Subsequently, 20mL of anhydrous toluene was added. The reaction mixture was refluxed under nitrogen for 48 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, toluene was evaporated under reduced pressure. The crude mixture was purified by silica gel column chromatography to isolate 130mg of product (isolated yield=47%).
1 H-NMR(400MHz,CDCl 3 ,δ)δ7.74-7.35(m,22H),7.18-7.05(m,8H),6.80(d,J＝8.4Hz,8H),6.49-6.44(m,2H),4.23(t,J＝5.6Hz,1H),3.78(s,13H),1.46(q,J＝7.2Hz,2H),1.42-1.27(m,7H),0.93(dt,J＝20.2,7.2Hz,6H)。
Synthesizing BT-thiadiazole:
synthesis of 4,8- (2-ethyl-1-hexyloxy) benzodithiophene 2
To a suspension of benzodithiophene-4, 8-dione (2 g,9.08mmol,1.0 eq.) in DMF was added KOH pellets (10.1 g,181.6mmol,20 eq.) and zinc (10.1 g,154.3mmol,17 eq.) and stirred at 85℃for 24 hours. After 24 hours, the reaction mixture was cooled to room temperature, 1-bromo-2-ethylhexane was added and stirred at 85 ℃ for an additional 24 hours. The reaction mixture was cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure. The crude mixture was purified by silica gel column chromatography to isolate 843mg of product (isolated yield=21%).
1 H-NMR (400 MHz, acetone-d) 6 ,δ)7.64(d,J＝5.5Hz,2H),7.55(d,J＝5.6Hz,2H),4.23(d,J＝5.3Hz,4H),1.86-1.33(m,19H),1.03(t,J＝7.4Hz,6H),0.98-0.90(m,6H)。
13 C-NMR (101 MHz, acetone-d) 6 ,δ)145.48,132.27,130.93,127.67,120.98,76.63,41.59,31.26,29.97,24.62,23.77,14.40,11.66。
Synthesis of 2-bromo-4, 8- (2-ethyl-1-hexyloxy) benzodithiophene 3
4,8- (2-ethyl-1-hexyloxy) benzodithiophene 2 (200 mg,0.4477mmol,1 eq.) was placed in a round bottom flask. N-bromosuccinimide (80 mg,0.4494mmol,1 eq.) was added. Next, 5mL of anhydrous dichloromethane was added under nitrogen. Then 0.8mL of glacial acetic acid was slowly added at room temperature. The reaction mixture was stirred at room temperature overnight. The reaction was then subjected to thin layer chromatography. After stirring for 12 hours, the reaction mixture was quenched by the addition of deionized water. The organic layer was separated. The aqueous layer was extracted with dichloromethane (3X 10 mL). The combined organic layers were washed with saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 107mg of product (isolated yield = 40%).
1 H NMR (400 MHz, acetone-d) 6 ,δ)7.71(d,J＝5.6Hz,1H),7.62(s,1H),7.56(d,J＝5.6Hz,1H),4.23(t,J＝5.4Hz,4H),1.87-1.32(m,19H),1.02(t,J＝7.5Hz,6H),0.94(t,J＝7.1Hz,6H)。
Synthesis of 2- (N, N-diphenylamine) -4, 8-bis (2-ethyl-1-hexyloxy) benzodithiophene 5
2-bromo-4, 8-bis (2-ethyl-1-hexyloxy) benzodithiophene 5 (93 mg,0.1769mmol,1.0 eq.) was placed in a round bottom flask. N, N-4-methoxydiphenylamine (48 mg,0.2123mmol,1.2 eq), tris (dibenzylideneacetone) dipalladium [0] (3 mg,0.0035mmol,0.02 eq.) tris-tert-butylphosphine (0.02 mL 10% W/W solution, 0.0070 mmol,0.04 eq.) and sodium tert-butoxide (20 mg,0.2123mmol,1.2 eq.) were added. Next, 5mL of anhydrous toluene was added. The reaction mixture was stirred at reflux for 24 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature and deionized water was added. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 5 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 105mg of product (isolated yield = 88%).
1 H-NMR (400 MHz, acetone-d) 6 ,δ)7.48-7.41(m,2H),7.30-7.25(m,4H),6.99-6.94(m,4H),6.43(s,1H),4.05(dd,J＝38.7,5.1Hz,4H),3.81(s,6H),1.72-1.24(m,18H),0.98-0.81(m,12H)。
Synthesis of trimethyltin derivative 6
2- (N, N-Diphenylamine) -4, 8-diphenylbenzodithiophene 5 (100 mg,0.1567mmol,1.0 eq.) was placed in a dry round bottom flask. 55mL of anhydrous THF was added. The reaction mixture was cooled to-78 ℃. Next, n-BuLi (2.5M, 0.326mL,0.839mmol,1.1 eq.) was slowly added and stirred at the same temperature for 2 hours. After 2 hours, the reaction mixture was warmed to 0 ℃ and stirred for 15 minutes. Then, it was further cooled to-78 ℃. Trimethyltin chloride (1 m,0.203ml,0.2037mmol,1.3 eq.) was added. It was stirred at the same temperature for 4 hours. Then, the temperature was slowly warmed to room temperature and stirred at room temperature for another 12 hours. Then, it was quenched by addition of water. 10mL of ethyl acetate was added. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 10 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure to give a crude material. The product was confirmed by NMR of the crude material. It was used as such in the next step without further purification.
Synthesis of BT-thiadiazole 8
Trimethyltin derivative 6 (124 mg,0.1502mmol,2.1 eq.) was placed in a round bottom flask. 4, 7-Dibromobenzothiadiazole (21 mg,0.0714mmol,1.0 eq.) and tetrakis (triphenylphosphine) palladium [0] (8 mg,0.0071mmol,0.01 eq.) were added. Next, 5mL of anhydrous toluene was added. The reaction mixture was refluxed under nitrogen for 48 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, toluene was evaporated under reduced pressure. The crude mixture was purified by silica gel column chromatography to isolate 65mg of the product (isolated yield=59%).
1 H-NMR(600MHz,CDCl 3 ,δ)8.79(s,2H),7.91(s,2H),7.25(d,J＝6.5Hz,8H),6.92-6.84(m,8H),6.54(s,2H),4.13(dd,J＝79.1,5.4Hz,8H),3.83(s,12H),1.80(p,J＝6.0Hz,2H),1.76-1.64(m,6H),1.46-1.26(m,23H),1.03(t,J＝7.4Hz,7H),0.98-0.87(m,19H)。
13 C-NMR(151MHz,CDCl 3 ,δ)156.80,140.29,126.22,114.63,76.12,55.49,40.65,40.51,30.52,30.43,29.22,29.13,23.86,23.78,23.17,23.07,14.17,14.13,11.38,11.2
Detailed description of the synthesis of the Azafulvene structure:
scheme 1: general scheme for the Synthesis of Az-H, az-OMe and Az-OHEX
Synthesis of N, N-4-methoxy-diphenylamine 3b
In a clean round bottom flask, p-methoxyaniline (10 g,81.2mmol,1 eq.), tris (dibenzylideneacetone) dipalladium [0] (372 mg,0.406mmol,0.5 mol%) and 1,1' -bis (diphenylphosphino) ferrocene (450 mg,0.812mmol,1 mol%) were added. Sodium tert-butoxide (7.8 g,81.2mmol,1.0 eq.) was added. To this mixture was added anhydrous toluene (200 mL). Subsequently, 1-bromo-4-methoxybenzene was added. The mixture was stirred under reflux for 1.5 hours. The reaction was monitored by thin layer chromatography. After the reaction, it was quenched by addition of deionized water. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 50 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure in a rotary evaporator. It was further dissolved in a minimum amount of dichloromethane. The product was washed out by addition of hexane and filtered to isolate 15.4g of product 7 (yield=83%).
1 H-NMR(400MHz,CDCl 3 ,δ)6.98-6.89(m,4H),6.85-6.79(m,4H),5.27(s,1H),3.78(s,6H)。
13 C-NMR(101MHz,CDCl 3 )δ153.45,137.13,118.73,113.90,54.82。
Synthesis of N, N-4-hexyloxydiphenylamine 3c
In a clean round bottom flask, p- (hexyloxy) aniline (4 g,19.3mmol,1 eq.), tris (dibenzylideneacetone) dipalladium [0] (75 mg,0.0819mmol,0.4 mol%) and 1,1' -bis (diphenylphosphino) ferrocene (282 mg,0.509mmol,2.6 mol%) were added. Sodium tert-butoxide (1.95 g,20.2mmol,1.05 eq.) was added. To this mixture was added anhydrous toluene (200 mL). Subsequently, 1-bromo-4-hexyloxybenzene was added. The mixture was stirred under reflux for 1.5 hours. The reaction was monitored by thin layer chromatography. After the reaction, it was quenched by addition of deionized water. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 30 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure in a rotary evaporator. It was further dissolved in a minimum amount of dichloromethane. The product was washed out by addition of hexane and filtered to isolate 4.6g of product 7 (yield=61%).
1 H-NMR (400 MHz, acetone-d) 6 ,δ)6.98-6.93(m,4H),6.84-6.78(m,4H),6.72(s,1H),3.92(t,J＝6.5Hz,4H),1.78-1.68(m,4H),1.51-1.42(m,4H),1.41-1.28(m,8H),0.97-0.82(m,6H)。
13 C NMR (101 MHz, acetone-d) 6 )δ154.19,139.31,119.55,116.12,68.90,32.38,30.17,26.52,23.31,14.31。
Synthesis of N, N-bis (4-methoxyphenyl) -4-bromoaniline 5b
N, N-4-methoxydiphenylamine 3b (6 g,26.16mmol,1.0 eq.) was placed in a round bottom flask. 1-bromo-4-iodobenzene (8.8 g,31.4mmol,1.2 eq), tris (dibenzylideneacetone) dipalladium [0] (256 mg,0.2473mmol,0.01 eq.), 1' -bis (diphenylphosphino) ferrocene (2793 mg,0.494mmol,0.02 eq.) and sodium tert-butoxide (3.8 g,39.26mmol,1.5 eq.) were added. Subsequently, 40mL of anhydrous toluene was added. The reaction mixture was stirred at reflux for 24 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature and deionized water was added. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 8.2g of product (isolated yield = 82%).
1 H-NMR(400MHz,CDCl 3 ,δ)7.24(d,J＝8.5Hz,2H),7.03(d,J＝8.0Hz,4H),6.89-6.71(m,6H),3.79(s,6H)。
Synthesis of N, N-bis (4-hexyloxyphenyl) -4-bromoaniline 5c
N, N-4-methoxydiphenylamine 3c (2 g,5.03mmol,1.0 eq.) was placed in a round bottom flask. 1-bromo-4-iodobenzene (1.57 g,5.53mmol,1.1 eq), tris (dibenzylideneacetone) dipalladium [0] (46 mg,0.050mmol,0.01 eq.), 1' -bis (diphenylphosphino) ferrocene (56 mg,0.100mmol,0.02 eq.) and sodium t-butoxide (0.725 mg,7.55mmol,1.5 eq.) were added. Subsequently, 25mL of anhydrous toluene was added. The reaction mixture was stirred at reflux for 24 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature and deionized water was added. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 2.4g of product (isolated yield = 86%).
1 H NMR (400 MHz, acetone-d) 6 ,δ)7.33-7.24(m,2H),7.10-6.99(m,4H),6.95-6.86(m,4H),6.78-6.71(m,2H),3.98(t,J＝6.5Hz,4H),1.81-1.71(m,4H),1.53-1.41(m,4H),1.41-1.25(m,8H),0.99-0.82(m,6H)。
Synthesis of 1- (N, N-diphenyl) -4-1H-pyrrolobenzene 6a
Anhydrous zinc chloride (2.53 g,18.5mmol,3.0 eq.) was placed in a dry round bottom Schlenk flask (Schlenk flash) and 25mL of anhydrous THF was added under nitrogen. In another dry schlenk flask, sodium hydride (444 mg,18.5mmol,3.0 eq) was weighed and 12mL of anhydrous THF was added under nitrogen. The mixture was cooled to 0 ℃ and pyrrole (2 ml,18.5mmol,3 eq.) was added followed by stirring for 15 minutes to form sodium pyrrolidine. After 15 minutes, the zinc chloride solution was cannulated into the sodium pyrrolidine solution and stirred for an additional 15 minutes. Next, 4-bromotriphenylamine (2 g,6.17mmol,1 eq.) palladium acetate (55 mg,0.2467mmol,0.04 eq.) and tri-tert-butylphosphonium tetrafluoroborate (143 mg,0.4935mmol,0.08 eq.) were added under nitrogen. The reaction mixture was refluxed for 20 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature. Deionized water and 20mL ethyl acetate were added. Undissolved particles were filtered through celite. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 1.9g of product (isolated yield = 52%).
1 H-NMR (400 MHz, acetone-d) 6 ,δ)10.42(s,1H),7.56(ddt,J＝8.4,4.7,1.9Hz,2H),7.34-7.21(m,4H),7.10-6.97(m,8H),6.83(ddq,J＝5.7,2.5,1.4Hz,1H),6.47(dddt,J＝4.1,3.3,2.5,1.3Hz,1H),6.18-6.12(m,1H)。
13 C-NMR (101 MHz, acetone-d) 6 ,δ)147.84,145.40,131.44,129.29,128.54,124.59,124.50,123.76,122.66,118.67,109.24,105.09。
Synthesis of 1- (N, N-4-methoxydiphenyl) -4-1H-pyrrolobenzene 6b
Anhydrous zinc chloride (2.13 g,15.61mmol,3.0 eq.) was placed in a dry round bottom schlenk flask and 25mL anhydrous THF was added under nitrogen. In another dry schlenk flask, sodium hydride (374 mg,15.61mmol,3.0 eq.) is weighed and 12mL of anhydrous THF is added under nitrogen. The mixture was cooled to 0deg.C and pyrrole (1.08 mL,15.61mmol,3 eq.) was added followed by stirring for 15 minutes to form sodium pyrrolidine. After 15 minutes, the zinc chloride solution was cannulated into the sodium pyrrolidine solution and stirred for an additional 15 minutes. Next, N-bis (4-methoxyphenyl) -4-bromoaniline (2 g,5.2mmol,1 eq.) palladium acetate (47 mg,0.2081mmol,0.04 eq.) and tri-tert-butylphosphonium tetrafluoroborate (73 mg,0.4161mmol,0.08 eq.) were added under nitrogen. The reaction mixture was refluxed for 20 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature. Deionized water and 20mL ethyl acetate were added. Undissolved particles were filtered through celite. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 1.5g of product (isolated yield = 72%).
1 H NMR (500 MHz, chloroform-d, δ) 8.32 (s, 1H), 7.28 (dd, j=7.6, 5.6hz, 2H), 7.05 (dd, j=9.0, 2.1hz, 4H), 6.97-6.91 (m, 2H), 6.82 (dd, j=7.6, 5.4hz, 5H), 6.40 (d, j=3.7 hz, 1H), 6.27 (q, j=2.9 hz, 1H), 3.80 (s, 6H).
13 C NMR
Synthesis of 1- (N, N-4-hexyloxydiphenyl) -4-1H-pyrrolobenzene 6c
Anhydrous zinc chloride (1.78 g,13.03mmol,3.0 eq.) was placed in a dry round bottom schlenk flask and 25mL anhydrous THF was added under nitrogen. In another dry schlenk flask, sodium hydride (0.3127 mg,13.03mmol,3.0 eq) is weighed and 15mL of anhydrous THF is added under nitrogen. The mixture was cooled to 0 ℃ and pyrrole (0.284 ml,13.03mmol,3 eq.) was added followed by stirring for 15 minutes to form sodium pyrrolidine. After 15 minutes, the zinc chloride solution was cannulated into the sodium pyrrolidine solution and stirred for an additional 15 minutes. Next, a solution of N, N-bis (4-hexyloxyphenyl) -4-bromoaniline in 15mL of anhydrous THF (2.4 g,4.34mmol,1 eq.) was transferred using a catheter, and palladium acetate (47 mg,0.2081mmol,0.04 eq.) and tri-tert-butylphosphonium tetrafluoroborate (73 mg,0.4161mmol,0.08 eq.) were added under nitrogen. The reaction mixture was refluxed for 20 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature. Deionized water and 20mL ethyl acetate were added. Undissolved particles were filtered through celite. The organic layer was separated. The aqueous layer was extracted with ethyl acetate (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure on a rotary evaporator and purified by silica gel column chromatography to isolate 2.28g of product (isolated yield=67%).
1 H-NMR (400 MHz, acetone-d) 6 ,δ)δ10.32(s,1H),7.48-7.43(m,2H),7.04-6.97(m,4H),6.91-6.84(m,6H),6.79(td,J＝2.7,1.5Hz,1H),6.38(ddd,J＝3.5,2.6,1.5Hz,1H),6.12(ddd,J＝3.5,2.7,2.3Hz,1H),3.97(s,4H),1.82-1.71(m,4H),1.54-1.41(m,4H),1.36(dddd,J＝8.0,6.9,3.9,2.4Hz,8H),0.95-0.86(m,6H)。
13 C-NMR (101 MHz, acetone-d) 6 ,δ)155.41,146.64,140.82,131.72,126.26,126.08,124.20,121.03,118.08,115.16,108.99,104.30,67.79,31.36,25.51,22.30,13.31。
Synthesis of diketone precursor 7a
To a dry round bottom schlenk flask was added 15mL of anhydrous dichloromethane under nitrogen. Subsequently, oxalyl chloride (0.14 ml,1.6mmol,1.0 eq.) was added and the reaction mixture was cooled to-78 ℃. To this mixture was added anhydrous pyridine (0.26 ml,3.2mmol,2.0 eq.) and stirred at the same temperature for an additional 40 minutes. Next, a solution of 1- (N, N-diphenyl) -4-1H-pyrrolobenzene 4a (1 g,3.2mmol,2.0 eq.) in 15mL anhydrous dichloromethane was transferred using a cannula.
The reaction mixture was stirred at the same temperature for an additional 15 minutes. The mixture was warmed to room temperature. The reaction mixture was quenched by the addition of water. The organic layer was separated. The aqueous layer was extracted with dichloromethane (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure in a rotary evaporator and purified by basic alumina column chromatography to isolate 546mg of product (isolated yield=51%).
1 H-NMR (400 MHz, acetone-d) 6 ,δ)11.21(s,2H),7.86(d,J＝8.7Hz,4H),7.37-7.33(m,8H),7.17-7.03(m,20H),6.70(dd,J＝4.1,2.5Hz,2H)。
Synthesis of diketone precursor 7b:
to a dry round bottom schlenk flask was added 15mL of anhydrous dichloromethane under nitrogen. Subsequently, oxalyl chloride (0.058 mL,0.67mmol,1.0 eq.) was added and the reaction mixture was cooled to-78 ℃. To this mixture was added anhydrous pyridine (0.11 ml,1.35mmol,2.0 eq.) and stirred at the same temperature for an additional 40 minutes. Next, a solution of 1-bis (N, N-4-methoxyphenyl) -4-1H-pyrrolobenzene 4b (0.5 g,1.35mmol,2.0 eq.) in 15mL of anhydrous dichloromethane was transferred using a cannula. The reaction mixture was stirred at the same temperature for an additional 15 minutes. The mixture was warmed to room temperature. The reaction mixture was quenched by the addition of water. The organic layer was separated. The aqueous layer was extracted with dichloromethane (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure in a rotary evaporator and purified by basic alumina column chromatography to isolate 300mg of product (isolated yield = 56%).
1 H-NMR (600 MHz, acetone-d) 6 ,δ)11.12(s,2H),7.80-7.72(m,4H),7.18-7.05(m,10H),6.97-6.92(m,8H),6.90-6.84(m,4H),6.62(dd,J＝4.1,2.5Hz,2H),3.80(s,12H)。
13 C-NMR (151 MHz, acetone-d) 6 ,δ)180.74,157.64,150.15,142.11,141.02,130.87,128.16,127.34,123.17,119.94,115.77,108.97,55.76。
Synthesis of diketone precursor 7c
To a dry round bottom schlenk flask was added 10mL of anhydrous dichloromethane under nitrogen. Subsequently, oxalyl chloride (0.084 mL,0.9848mmol,1.0 eq.) was added and the reaction mixture was cooled to-78 ℃. To this mixture was added anhydrous pyridine (0.16 ml,1.97mmol,2.0 eq.) and stirred at the same temperature for an additional 40 minutes. Next, a solution of 1-bis (N, N-4-hexyloxydiphenyl) -4-1H-pyrrolobenzene 4c (1.06 g,1.97mmol,2.0 eq.) in 10mL of anhydrous dichloromethane was transferred using a cannula. The reaction mixture was stirred at the same temperature for an additional 15 minutes. The mixture was warmed to room temperature. The reaction mixture was quenched by the addition of water. The organic layer was separated. The aqueous layer was extracted with dichloromethane (3X 20 mL). The combined organic layers were washed with brine solution and dried over anhydrous sodium sulfate. The crude mixture was concentrated under reduced pressure in a rotary evaporator and purified by basic alumina column chromatography to isolate 465mg of product (isolated yield = 46%).
1 H-NMR (600 MHz, acetone-d) 6 ,δ)11.09(s,2H),7.85-7.66(m,4H),7.20-7.02(m,10H),6.96-6.92(m,8H),6.89-6.85(m,4H),6.63(dd,J＝4.0,2.5Hz,2H),4.00(t,J＝6.5Hz,8H),1.80-1.75(m,8H),1.52-1.47(m,8H),1.38-1.33(m,16H),0.93-0.89(m,12H)。
Synthesis of BF 2 Bridged product 8a
Diketone precursor 5a (0.1 g,0.1482mmol,1 eq.) was placed in a pressure-resistant flask. 2mL of anhydrous THF was added under nitrogen, followed by 2, 6-di-tert-butylpyridine (1.5 mL,6.8mmol,46 eq.) and boron trifluoride etherate (1.1 mL,8.9mmol,60 eq.). The reaction mixture was stirred in a pressure-resistant flask at 100℃for 48 hours. After evaporation of the reaction solvent, the crude mixture was further dissolved in a minimum amount of dichloromethane. The product was precipitated in dichloromethane by the addition of methanol to isolate 74mg of product (yield=64%).
19 F-NMR (470 MHz, chloroform-d, delta) -139.73.
11 B-NMR (160 MHz, chloroform-d, delta) 0.47.
Synthesis of BF 2 Bridging product 8b
Diketone precursor 5b (0.32 g,0.4025mmol,1 eq.) was placed in a pressure-resistant flask. 12mL of anhydrous THF was added under nitrogen followed by 2, 6-di-tert-butylpyridine (5.4 mL,24.15mmol,60 eq.) and boron trifluoride etherate (2.37 mL,24.15mmol,60 eq.). The reaction mixture was stirred in a pressure-resistant flask at 100℃for 48 hours. After evaporation of the reaction solvent, the crude mixture was further dissolved in a minimum amount of dichloromethane. The product was a precipitated dichloromethane solution by the addition of methanol to isolate 281mg of product (yield=78%).
1 H NMR- (500 MHz, chloroform-d, δ) 7.93 (s, 4H), 7.59 (d, j=4.2 hz, 2H), 7.12 (d, j=24.6 hz, 10H), 6.92 (d, j=8.4 hz, 12H), 3.83 (s, 12H).
19 F-NMR (470 MHz, chloroform-d, delta) -153.98.
11 B-NMR (160 MHz, chloroform-d, delta) 4.11.
Synthesis of BF 2 Bridged product 8c
Diketone precursor 5c (0.411 g,0.4114mmol,1 eq.) was placed in a pressure-resistant flask. 2mL of anhydrous THF was added under nitrogen followed by 2, 6-di-tert-butylpyridine (4.09 mL,18.9mmol,46 eq.) and boron trifluoride etherate (3.04 mL,24.6mmol,60 eq.). The reaction mixture was stirred in a pressure-resistant flask at 100℃for 48 hours. The reaction solvent was evaporated. The crude mixture was further dissolved in a minimum amount of dichloromethane. The product was precipitated in methylene chloride by the addition of methanol to isolate 200mg of product (39% yield).
1 H-NMR (600 MHz, chloroform-d, delta) 7.99-7.77 (m, 4H), 7.27-7.10 (m, 16H), 6.91-6.87 (m, 8H), 3.96 (t, J=6.5 Hz, 8H), 1.82-1.75 (m, 8H), 1.53-1.45 (m, 8H), 1.41 (s, 4H), 1.36-1.29 (m, 14H), 1.01-0.81 (m, 12H).
19 F NMR (564 MHz, acetone-d) 6 ,δ)-151.95。
It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the present disclosure. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the disclosure. Thus, the disclosed compounds of the invention may include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the embodiments function are not intended to be limiting.

Claims (15)

1. A compound of the formula I,
wherein Don and Don' are each independently represented by formula a or formula B:
wherein, in formula a and formula B:
* Represents a bond to Acc;
# represents a bond to Z or Z';
each X is independently selected from the group consisting of: o, S, se, te, geRR ', CRR ', siRR ', and NR;
each Y is independently selected from the group consisting of: n and CR ";
R 1 、R 2 r, R' and R "independently represent hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and any two adjacent substituents are optionally joined to form a ring;
Acc is a divalent electron accepting group;
z and Z ' are each together a donor group D and D ' respectively or a acceptor group A and A ', respectively;
wherein each of Acc, Z and Z' may be further substituted with one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents are optionally joined to form a ring.
2. The compound of claim 1, wherein in formula I:
acc is an electron accepting group selected from the group consisting of: SO (SO) 2 、CF 2 Imines, ketones, polycyclic aromatic compounds, polycyclic heteroaromatic compounds, alkyl borates, aryl borates, alkoxy borates, and combinations thereof; d and D' are independently selected from the group consisting of: alkoxy, aryloxy, heteroaryloxy, alkenyloxy, alkyloxy, allyloxy, amino, dialkylamino, diarylamino, sulfanyl, thiiranyl, and combinations thereof; and
A and a' are independently selected from the group consisting of: halogen, NO 2 、CN、SO 2 R、CF 3 Imines, ketones, aldehydes, polycyclic aromatic compounds, polycyclic heteroaromatic compounds, alkyl borates, aryl borates, alkoxy borates, and combinations thereof; and
wherein each of Acc, Z and Z' may be further substituted with one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein any two adjacent substituents are optionally joined to form a ring.
3. The compound of claim 1, wherein the compound is represented by formula II:
wherein, in the formula II,
acc is a divalent electron accepting group selected from the group consisting of: polycyclic aromatic compounds, polycyclic heteroaromatic compounds, arylborates, alkoxyborates, and combinations thereof;
each X is independently selected from the group consisting of: o, S, se, te, geRR ', CRR ', siRR ', and NR;
Each Y is independently selected from the group consisting of: n and CR ";
z and Z ' are each together a donor group D and D ' respectively or a acceptor group A and A ', respectively;
d and D' are independently selected from the group consisting of: alkoxy, aryloxy, heteroaryloxy, alkenyloxy, alkyloxy, allyloxy, amino, dialkylamino, diarylamino, sulfanyl, thiiranyl, and combinations thereof;
a and a' are independently selected from the group consisting of: halogen, NO 2 、CN、SO 2 R、CF 3 Imines, ketones, aldehydes, polycyclic aromatic compounds, polycyclic heteroaromatic compounds, alkyl borates, aryl borates, alkoxy borates, and combinations thereof;
R 1 、R 1 '、R 2 、R 2 ', R, R ' and R ' independently represent hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
any two adjacent substituents are optionally joined to form a ring.
4. The compound of claim 1, wherein R 1 And R is 2 At least one of the following structuresIs represented by (a):
5. the compound of claim 1, wherein Acc is represented by one of the following structures:
wherein wavy lines represent bonds to Don and Don';
wherein each X independently represents O, S, se, NR 5 Or C (CN) 2 ；
Wherein Y and Z independently represent CR 4 And N;
wherein the method comprises the steps ofRepresents an optional aryl, heteroaryl, polyaromatic or polyheteroaryl ring condensate;
wherein R is 3 、R 4 、R 5 And R is 6 Independently represents hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein each R is 7 Independently an electron withdrawing group selected from the group consisting of: halogen, haloalkyl, aryl, heteroaryl, nitrile, and combinations thereof; and
wherein any two adjacent substituents are optionally joined to form a ring.
6. The compound of claim 1, wherein Z and Z' are independently represented by one of the following structures:
Wherein each X independently represents O, S, se, NR C Or C (CN) 2 ；
R A 、R B 、R C And R is D Independently represents hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents are optionally joined to form a ring.
7. The compound of claim 6, wherein Z and Z' are each an acceptor group selected from the group consisting of:
8. the compound of claim 6, wherein Z and Z' are each a donor group selected from the group consisting of:
9. the compound of claim 5, wherein Acc is selected from the group consisting of:
10. a compound represented by one of the following structures:
wherein, in formula C:
x is F, CF 3 、CN、SO 3 H or SO 2 Me; and
y is NH 2 、NMe 2 、NPh 2 、N(4-OMePh) 2 、N(3,4,5-(OMe)Ph) 2 Or N (2, 4,6- (OMe) Ph) 2 ；
11. An optoelectronic device comprising a compound of formula I:
wherein Don and Don' are each independently represented by formula a or formula B:
Wherein, in formula a and formula B:
* Represents a bond to Acc;
# represents a bond to Z or Z';
each X is independently selected from the group consisting of: o, S, se, te, geRR ', CRR ', siRR ', and NR;
each Y is independently selected from the group consisting of: n and CR ";
R 1 、R 2 r, R' and R "independently represent hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and any two adjacent substituents are optionally joined to form a ring;
acc is a divalent electron accepting group;
z and Z ' are each together a donor group D and D ' respectively or a acceptor group A and A ', respectively;
wherein each of Acc, Z and Z' may be further substituted with one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, sulfanyl, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;
Wherein any two adjacent substituents are optionally joined to form a ring.
12. The optoelectronic device of claim 11, wherein the optoelectronic device is selected from the group consisting of: organic light emitting devices OLED, organic phototransistors, organic photovoltaic cells, and organic photodetectors.
13. The optoelectronic device of claim 11, wherein the optoelectronic device is a photovoltaic cell.
14. A consumer product comprising the optoelectronic device of claim 11.
15. A formulation comprising the compound of claim 1.
CN202310641501.7A 2022-06-01 2023-06-01 Donor-acceptor-donor materials for optoelectronic applications Pending CN117143118A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US63/347,681 2022-06-01
US18/322,819 US20230391798A1 (en) 2022-06-01 2023-05-24 Donor-acceptor-donor type materials for optoelectronic applications
US18/322,819 2023-05-24

Publications (1)

Publication Number Publication Date
CN117143118A true CN117143118A (en) 2023-12-01

Family

ID=88885059

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310641501.7A Pending CN117143118A (en) 2022-06-01 2023-06-01 Donor-acceptor-donor materials for optoelectronic applications

Country Status (1)

Country Link
CN (1) CN117143118A (en)

Similar Documents

Publication Publication Date Title
Cho et al. Indolo [3, 2-b] indole-based crystalline hole-transporting material for highly efficient perovskite solar cells
KR102408338B1 (en) Organic electroluminescent materials and devices
KR101777883B1 (en) Materials for organic electroluminescence devices
EP2418033B1 (en) Metal complex and composition containing same
CN112789273A (en) Novel compound and organic light emitting device comprising same
JP2019501906A (en) Luminescent compound
EP3680261B1 (en) Polymer, coating composition comprising same, and organic light emitting element using same
CN114163424A (en) Organic electroluminescent material and device thereof
CN113631553B (en) Compound and organic light emitting device using the same
CN110835351A (en) Organic compound with pyrromethene boron complex as core and preparation and application thereof
EP3369731B1 (en) Heterocyclic compound and organic light emitting element comprising same
CN111247125B (en) Compound, coating composition comprising the same, and organic light emitting device
CN113039183B (en) Novel compound and organic light emitting device comprising the same
CN111094261A (en) Novel heterocyclic compound and organic light emitting device using the same
CN111868948B (en) Organic light emitting device
CN113227085A (en) Novel compound and organic light emitting device comprising same
WO2010082924A1 (en) Cross-linkable copper phthalocyanine complexes
JP2019508423A (en) Compound, composition and organic light emitting device
WO2017153731A1 (en) Dibenzofuran and dibenzothiophene derivatives and organic light-emitting devices containing them
KR20230064557A (en) Electroluminescent material and device thereof
KR20190114793A (en) Organic electroluminescence device
EP4190788A1 (en) Compound, hole transport material for photoelectric conversion element, hole transport layer, and photoelectric conversion element and solar cell using same
KR101545418B1 (en) Electroactive materials
EP3214152B1 (en) Silicon-based emitter compound
CN112079815B (en) Compound for organic photoelectric device, organic photoelectric device and display device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication