CN113292562A - Functional materials based on stable chemical structures - Google Patents

Abstract

The present application relates to functional materials based on stable chemical structures. A series of novel donor-acceptor type TADF activated emitters have been designed with the aim of developing stable OLEDs with enhanced operational stability and improved color purity. These materials can be used for full color display and lighting applications.

Description

Functional materials based on stable chemical structures

Cross Reference to Related Applications

Priority of united states provisional application No. 62/979,596, filed on 21/2/2020 and united states provisional application No. 63/044,434, filed on 26/6/2020, both of which are hereby incorporated by reference in their entireties.

Statement regarding federally sponsored research or development

The invention was made with government support according to DE-EE0005075 and DE-EE0008721 awarded by the Department of Energy. The government has certain rights in the invention.

Technical Field

The present application relates generally to donor-acceptor type latent functional materials.

Background

Photovoltaic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to make such devices are relatively inexpensive, and therefore 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 particular applications, such as fabrication on flexible substrates. Examples of organic optical electronic devices include Organic Light Emitting Diodes (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which the organic emissive layer emits light can generally be readily tuned with appropriate dopants.

In recent years, Organic Light Emitting Diodes (OLEDs) have attracted great attention in the scientific and industrial fields due to their outstanding advantages such as high color quality, wide viewing angle, low-cost manufacturing, low power consumption, fast response speed, and high electron-to-photon conversion efficiency. Most Organic Light Emitting Diodes (OLEDs) are phosphorescent OLEDs using iridium (Ir), palladium (Pd), and platinum (Pt) complexes because these metal complexes have strong Spin-Orbital Coupling (Spin-Orbital Coupling), which can efficiently emit light from their triplet excited state and achieve almost 100% internal efficiency. Thermally Activated Delayed Fluorescence (TADF) OLEDs are potentially capable of becoming a cheaper alternative to metal-based OLEDs due to their absence of precious metals and their operational stability.

Disclosure of Invention

There is provided a compound having the structure of formula I:

wherein:

T²and T³Represents a donor or an acceptor; t is¹Optionally represents a donor;

Y¹and Y²Each independently represents C, N, Si, B or P;

wherein when Y is¹And Y²When both represent C, then two radicals R¹May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

wherein if any two adjacent X^aAnd X^bRepresents X⁵-X⁸Wherein a and b are integers from 5 to 8, then two radicals R²May optionally be linked together to form a fused aryl group having the structure:

wherein if any two adjacent X^cAnd X^dRepresents X⁹-X¹²Where c and d are integers from 9 to 12, then two radicals R³May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹、X¹²、X¹³、X¹⁴、X¹⁵and X¹⁶Each independently represents C, N, Si, B or P;

U¹represents O, S, Se, NR²¹、P＝O、As＝O、Bi＝O、CR²¹R²²、C＝O、SiR²¹R²²、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O, or BiR²¹；

Each n is independently a valence-allowed integer; and is

R¹、R²、R³、R⁴、R⁵、R²¹And R²²Each independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof;

wherein two adjacent radicals R¹、R²、R³、R⁴、R⁵、R²¹、R²²Or combinations thereof may optionally be joined together to form fused rings.

According to another aspect, there is provided an Organic Light Emitting Diode (OLED) comprising a compound of formula I. According to another aspect, a light emitting device comprising a light emitting diode is provided.

Drawings

The following detailed description of the preferred embodiments will be better understood when read in conjunction with the appended drawings. For the purpose of illustration, there is shown in the drawings embodiments that are presently preferred. It should be understood, however, that the present disclosure is not limited to the precise arrangements and instrumentalities of the embodiments shown in the drawings.

Fig. 1 is a schematic view of an organic light emitting device.

Detailed Description

The present disclosure is directed, in part, to the unexpected discovery that donor-acceptor type latent functional materials have good operational stability.

Definition of

It is to be understood that the drawings and descriptions of the present disclosure have been simplified to illustrate elements that are relevant for a clear understanding of the present disclosure, while eliminating, for purposes of clarity, many other elements found in the art that are relevant to phosphorescent organic light-emitting devices and the like. One of ordinary skill in the art may recognize that other elements and/or steps are desirable and/or required in implementing the disclosed compositions and devices. However, because such elements and steps are well known in the art, and because they do not facilitate a better understanding of the present disclosure, a discussion of such elements and steps is not provided herein. The disclosure herein relates to all such variations and modifications to such elements and methods known to those skilled in the art.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described.

As used herein, each of the following terms has its associated meaning in this section.

The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. For example, "an element" means one element or more than one element.

When referring to a measurable value such as a quantity, duration, etc., as used herein, "about" is intended to encompass a deviation of ± 20%, 10%, 5%, 1% or 0.1% from the specified value, provided such deviation is appropriate.

Throughout this disclosure, various aspects may be presented in a range of forms. It is to be understood that the description in range format is merely for convenience and brevity and should not be construed as a fixed limitation on the scope of any composition or apparatus. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, descriptions of ranges such as from 1 to 6 should be considered to have the particular disclosed subranges, such as 1 to 3, 1 to 4,1 to 5, 2 to 4, 2 to 6,3 to 6, etc., as well as individual numbers within the ranges, e.g., 1,2, 2.7, 3,4, 5, 5.3, 6, and any full or partial increments therein. This applies regardless of the breadth of the range.

Headings are provided for convenience only and should not be construed as limiting the invention in any way. Embodiments described under any heading or in any section of this disclosure may be combined with embodiments described under that heading or under any other heading or in other sections of this disclosure.

Disclosed are the components used to prepare the compositions of the present disclosure, as well as the compositions themselves used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of various individual and collective combinations and permutations of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a variety of modifications that can be made to a plurality of molecules comprising the compound are discussed, each combination and permutation of the compound and the modifications that are possible are specifically contemplated unless specifically indicated to the contrary. Thus, if a class of molecules A, B and C and a class of molecules D, E and F are disclosed and an example of a combination molecule a-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated, meaning that the combinations a-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F are considered disclosed. Likewise, any subset or combination of these combinations is also disclosed. Thus, for example, a subset of A-E, B-F and C-E are considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions disclosed herein. Thus, if there are a number of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods.

The invention illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.

As mentioned herein, a linking atom or linking group may link two groups, for example N and C groups. If valency permits, the linking atom may optionally be attached to other chemical moieties. For example, in one aspect, once oxygen is bonded to two groups (e.g., N and/or C groups), no other chemical groups are attached because the valency is satisfied. In another aspect, when carbon is a linking atom, two additional chemical moieties may be attached to the carbon. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxy, alkyl, alkoxy, ═ O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

The term "cyclic structure" or similar terms used herein refer to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, and heterocyclyl.

As used herein, the term "substituted" is intended to include all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For suitable organic compounds, the permissible substituents can be one or more and can be the same or different. For purposes of this disclosure, a heteroatom (e.g., nitrogen) may have a hydrogen substituent and/or any permissible substituents of organic compounds described herein that satisfy the valences of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Also, the term "substituted" or "substituted with … …" includes the following implicit limitations: such substitutions are in accordance with permitted valences of the atoms and substituents being substituted, and the substitutions result in stable compounds, e.g., compounds that do not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.). It is also contemplated that, in certain aspects, individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted), unless expressly indicated to the contrary.

As used herein, the term "alkyl" is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. Alkyl groups may also be substituted or unsubstituted. For example, an alkyl group may be substituted with one or more groups (including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halo, hydroxy, nitro, silyl, sulfo-oxo, or thiol), as described herein. A "lower alkyl" group is an alkyl group containing one to six (e.g., one to four) carbon atoms.

Throughout this specification, "alkyl" is used generically to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl groups are also specifically referred to herein by identifying the particular substituent on the alkyl group. For example, the term "haloalkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halo groups (e.g., fluoro, chloro, bromo, or iodo). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, etc., as described below. When "alkyl" is used in one example and a specific term (e.g., "alkyl alcohol") is used in another example, it is not intended that the term "alkyl" nor that specific term be mentioned, such as "alkyl alcohol" or the like.

This practice is also applicable to the other groups described herein. That is, while terms such as "cycloalkyl" refer to unsubstituted and substituted cycloalkyl moieties, substituted moieties may be otherwise specifically identified herein; for example, a specifically substituted cycloalkyl group may be referred to as, for example, "alkylcycloalkyl". Similarly, substituted alkoxy groups may be specifically referred to as, for example, "halogenated alkoxy groups," and specifically substituted alkenyl groups may be, for example, "alkenyl alcohols" and the like. Moreover, practice of using generic terms (e.g., "cycloalkyl") and specific terms (e.g., "alkylcycloalkyl") is not intended to mean that the generic term does not include the specific term.

As used herein, the term "cycloalkyl" is a carbon-based non-aromatic ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like. The term "heterocycloalkyl" is a type of cycloalkyl group as defined above and is included within the meaning of the term "cycloalkyl" in which at least one carbon atom in the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkyl and heterocycloalkyl groups may be substituted or unsubstituted. Cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halo, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.

As used herein, the term "polyalkylene" is a compound having two or more CH groups attached to each other₂The radical of (a). The polyalkylene group may be represented by the formula- (CH)₂)_a-represents, wherein "a" is an integer from 2 to 500.

As used herein, the terms "alkoxy" and "alkoxy" refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as-OA¹Wherein A is¹Is alkyl or cycloalkyl as defined above. "alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether, such as-OA¹-OA²or-OA¹-(OA²)_a-OA³Wherein "a" is an integer from 1 to 200 and A¹、A²And A³Is an alkyl and/or cycloalkyl group.

As used herein, the term "alkenyl" is a hydrocarbon group having 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures, e.g. (A)¹A²)C＝C(A³A⁴) It is desirable to include both E and Z isomers. This can be inferred from the structural formula herein where an asymmetric olefin is present, or it can be explicitly indicated by the bond symbol C ═ C. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halo, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo, or thiol as described herein.

As used herein, the term "cycloalkenyl" is a non-aromatic carbon-based ring consisting of at least three carbon atoms and containing at least one carbon-carbon double bond (i.e., C ═ C). Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is one type of cycloalkenyl group as defined above, and is included within the meaning of the term "cycloalkenyl", where at least one carbon atom in the ring is replaced with a heteroatom such as (but not limited to) nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups may be substituted or unsubstituted. The cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

As used herein, the term "alkynyl" is a hydrocarbon group having from 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halo, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo, or thiol as described herein.

As used herein, the term "cycloalkynyl" is a non-aromatic carbon-based ring, which is composed of at least seven carbon atoms and contains at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is one type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one carbon atom in the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl may be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silane, sulfonate-oxo, or thiol as described herein.

As used herein, the term "aryl" is a group containing any carbon-based aromatic group, including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom incorporated within the ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" is also included in the term "aryl", which defines a group containing an aromatic group that does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halo, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo, or thiol as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together by a fused ring structure, such as naphthalene, or linked by one or more carbon-carbon bonds, such as biphenyl.

As used herein, the term "aldehyde" is represented by the formula-C (O) H. Throughout the specification, "C (O)" is a shorthand symbol for carbonyl, i.e., C ═ O.

As used herein, the term "amine" or "amino" is represented by the formula-NA¹A²Is shown in the specification, wherein A¹And A²May independently be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.

As used herein, the term "alkylamino" is represented by the formula-NH (-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl) amino, (tert-butyl) amino, pentylamino, isopentylamino, (tert-pentyl) amino, hexylamino, and the like.

As used herein, the term "dialkylamino" is of the formula-N (-alkyl)₂Wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (sec-butyl) amino, di (tert-butyl) amino, dipentylamino, diisopentylamino, di (tert-pentyl) amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

As used herein, the term "carboxylic acid" is represented by the formula-C (O) OH.

As used herein, the term "ester" is represented by the formula-OC (O) A¹or-C (O) OA¹Is shown in the specification, wherein A¹May be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. As used herein, the term "polyester" is represented by the formula- (A)¹O(O)C-A²-C (O) or- (A)¹O(O)C-A²-OC(O))_a-is represented by, wherein A¹And A²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orHeteroaryl, and "a" is an integer from 1 to 500. "polyester" is used as a term to describe a group resulting from the reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxyl groups.

As used herein, the term "ether" is represented by formula A¹OA²Is shown in the specification, wherein A¹And A²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. As used herein, the term "polyether" is represented by the formula- (A)¹O-A²O)_a-is represented by, wherein A¹And A²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

As used herein, the term "halide" refers to the halogens fluorine, chlorine, bromine, and iodine.

As used herein, the term "heterocyclyl" refers to monocyclic and polycyclic non-aromatic ring systems and as used herein, "heteroaryl" refers to monocyclic and polycyclic aromatic ring systems: wherein at least one ring member is not carbon. The terms include azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole (including 1,2, 3-oxadiazole, 1,2, 5-oxadiazole and 1,3, 4-oxadiazole), piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine (including 1,2,4, 5-tetrazine), tetrazole (including 1,2,3, 4-tetrazole and 1,2,4, 5-tetrazole), thiadiazole (including 1,2, 3-thiadiazole, 1,2, 5-thiadiazole and 1,3, 4-thiadiazole), thiazole, thiophene, triazine (including 1,3, 5-triazine and 1,2, 4-triazine), triazole (including 1,2, 3-triazole, and triazole, 1,3, 4-triazole), and the like.

As used herein, the term "hydroxy" is represented by the formula-OH.

The term "ketone" as used herein is represented by formula A¹C(O)A²Is shown in the specification, wherein A¹And A²May independently be alkyl, cycloalkyl, alkenyl, cycloalkene, as described hereinA group, an alkynyl group, a cycloalkynyl group, an aryl group or a heteroaryl group.

As used herein, the term "azido" is represented by the formula-N₃And (4) showing.

As used herein, the term "nitro" is defined by the formula-NO₂And (4) showing.

As used herein, the term "nitrile" is represented by the formula-CN.

As used herein, the term "ureido" refers to the formula-NHC (O) NH₂Or ureido of-NHC (O) -NH-.

As used herein, the term "phosphoramide" refers to the formula-P (O) (NA)¹A²)₂A group of (A), wherein¹And A²May independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.

As used herein, the term "carbamoyl" refers to a compound having the formula-CONA¹A²Amide group of (A), wherein¹And A²May independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.

As used herein, the term "sulfamoyl" refers to compounds of the formula-S (O)₂NA¹A²A group of (A), wherein¹And A²May independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.

As used herein, the term "silyl" is defined by the formula-SiA¹A²A³Is shown in the specification, wherein A¹、A²And A³May independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.

As used herein, the term "sulfo-oxo" is represented by the formula-S (O) A¹、-S(O)₂A¹、-OS(O)₂A¹or-OS (O)₂OA¹Is shown in the specification, wherein A¹Is hydrogen or alkyl, cycloalkyl, alkenyl, cyclic as described hereinAlkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl. Throughout the present specification, "S (O)" is a shorthand notation of S ═ O. The term "sulfonyl" as used herein refers to a compound of the formula-S (O)₂A¹A sulfonic acid-oxo group represented by wherein A¹Is hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. The term "sulfone," as used herein, is represented by formula A¹S(O)₂A²Is shown in the specification, wherein A¹And A²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide", as used herein, is represented by formula A¹S(O)A²Is shown in the specification, wherein A¹And A²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

As used herein, the term "thiol" is represented by the formula-SH.

As used herein, "R", "A", "R", "A", "R", "A", "R¹”、“R²”、“R³”、“Rⁿ"(where n is an integer) may independently include hydrogen or one or more of the groups listed above. For example, if R¹Is a straight chain alkyl group, one hydrogen atom in the alkyl group may be optionally substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halo group, or the like. Depending on the group selected, the first group may be incorporated into the second group, or alternatively, the first group may be pendant (i.e., attached) to the second group. For example, for the phrase "alkyl group comprising an amino group," the amino group can be incorporated within the alkyl backbone. Alternatively, the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.

As used herein, a compound of the present disclosure may contain an "optionally substituted" moiety. In general, the term "substituted," whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at each position. The combinations of substituents contemplated by the present disclosure are preferably those that result in the formation of stable or chemically feasible compounds. It is also contemplated that, in certain aspects, individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted), unless expressly indicated to the contrary.

In some aspects, the structure of a compound may be represented by the formula:

it is understood that it is equivalent to the following formula:

where n is typically an integer. That is, RⁿIs understood to represent five independent substituents R^n(a)、R^n(b)、R^n(c)、R^n(d)、R^n(e). By "independent substituents" is meant that each R substituent may be independently defined. For example, if R^n(a)In one example, halogen, then R^n(b)In that case not necessarily halogen.

R, R is referred to multiple times in the chemical structures and parts disclosed and described herein¹、R²、R³、R⁴、R⁵、R⁶And the like. Pair R, R in the specification¹、R²、R³、R⁴、R⁵、R⁶Etc. are applicable to statement R, R, respectively¹、R²、R³、R⁴、R⁵、R⁶Etc. to any structure or portion thereof.

Compound (I)

The compounds disclosed herein are suitable for a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as daylight sensitive and photosensitive devices, Organic Light Emitting Devices (OLEDs), light emitting devices, or devices capable of both light absorption and light emission and as markers for biological applications.

The compounds disclosed herein are suitable for use in a variety of applications. As the light emitting material, the compound is applicable to Organic Light Emitting Devices (OLEDs), light emitting devices, and displays, as well as other light emitting devices.

In another aspect, the compounds can provide improved efficiency, improved operating life, or both of a lighting device (e.g., an organic light emitting device) as compared to conventional materials.

The compounds of the present disclosure can be made using a variety of methods, including but not limited to those described in the examples provided herein.

Compounds of the invention

In one aspect, the disclosure relates to compounds of formula I:

wherein:

T²and T³Represents a donor or an acceptor; t is¹Optionally represents a donor;

Y¹and Y²Each independently represents C, N, Si, B or P;

wherein when Y is¹And Y²When both represent C, then two radicals R¹May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

wherein if any two adjacent X^aAnd X^bRepresents X⁵-X⁸Wherein a and b are integers from 5 to 8, then two radicals R²Can be optionally connected togetherForming a fused aryl group having the structure:

wherein if any two adjacent X^cAnd X^dRepresents X⁹-X¹²Where c and d are integers from 9 to 12, then two radicals R³May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

wherein:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹、X¹²、X¹³、X¹⁴、X¹⁵and X¹⁶Each independently represents C, N, Si, B or P;

U¹represents O, S, Se, NR²¹、P＝O、As＝O、Bi＝O、CR²¹R²²、C＝O、SiR²¹R²²、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O, or BiR²¹；

Each n is independently a valence-allowed integer; and is

R¹、R²、R³、R⁴、R⁵、R²¹And R²²Each independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, ringAlkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymers; or any conjugate or combination thereof;

wherein two adjacent radicals R¹、R²、R³、R⁴、R⁵、R²¹、R²²Or combinations thereof may optionally be joined together to form fused rings.

In one embodiment, the disclosure relates to compounds wherein one or more of the following conditions are true:

(i)Y¹and Y²Each is C, and two radicals R¹Represented by one of the following structures, wherein the dotted line represents Y attached to formula I¹And Y²The bond of (a):

(ii) for two adjacent X^aAnd X^bBy two radicals R²Represented by one of the following structures, wherein the dotted line represents X attached to formula I^aAnd X^bThe bond of (a):

(iii) for two adjacent X^cAnd X^dBy two radicals R³Represented by one of the following structures, wherein the dotted line represents X attached to formula I^cAnd X^dThe bond of (a):

wherein:

X¹³、X¹⁴、X¹⁵、X¹⁶、X¹⁷、X¹⁸、X¹⁹and X²⁰Each independently represents C, N, Si, B or P;

each U¹And U²Denotes O, S, Se, P-O, As-O, Bi-O, CR²¹R²²、C＝O、SiR²¹R²²、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O, or BiR²¹；

Each R⁴、R⁵、R⁶And R⁷Independently absent or present as a single substituent or multiple substituents where valency permits, and R⁴、R⁵、R⁶、R²¹And R²²Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any affix thereofA compound or combination;

any two adjacent R⁴、R⁵、R⁶、R⁷Or combinations thereof may optionally be joined together to form fused rings; and is

Each occurrence of n is independently a valence-permitting integer.

In one embodiment, the disclosure relates to compounds wherein one or more of the following conditions are true:

(i)Y¹and Y²At least one of (A) represents C, and at least one R represents¹Represented by the following structure:

(ii) at least one R²Represented by the following structure:

(iii) at least one R³Represented by the following structure:

wherein:

the dotted line represents a bond to formula I;

X¹³、X¹⁴、X¹⁵、X¹⁶、X¹⁷、X¹⁸、X¹⁹and X²⁰Each independently represents C, N, Si, B or P;

U¹represents N, P, As, B, Al or Bi, CR²¹、SiR²¹、GeR²¹、P＝O、As＝O、B、Bi＝O、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、R²¹Bi ═ O, or BiR²¹；

Each R⁴、R⁵And R⁶Independently absent or present as a single substituent or multiple substituents where valency permits, and R⁴、R⁵、R⁶、R²¹And R²²Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof;

any two adjacent R⁴、R⁵、R⁶Or combinations thereof may be optionally joined to form fused rings; and is

Each occurrence of n is independently a valence-permitting integer.

In one embodiment, X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹And X¹²Represents N.

In one embodiment, X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹And X¹²Represents N.

In one embodiment, X⁵、X⁶、X⁷And X⁸At least one of them represents N, and X⁹、X¹⁰、X¹¹And X¹²Represents N.

In one embodiment, the compound is represented by formula II, formula III, formula IV, formula V, or formula VI;

wherein:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹and X¹²Each independently represents C, N, Si, B or P;

Y¹and Y²Each independently represents C, N, Si, B or P;

each occurrence of n is independently a valence-permitting integer; and is

R¹、R²And R³Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof; and is

Any two adjacent R¹、R²、R³Or combinations thereof may optionally be joined together to form fused rings.

In one embodiment, the compound is represented by one of the following structures:

wherein X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹、X¹²、X¹³、X¹⁴、X¹⁵、X¹⁶、X¹⁷、X¹⁸、X¹⁹、X²⁰、X²¹、X²²、X²³、X²⁴、X²⁵、X²⁶、X²⁷And X²⁸Each independently represents C, N, Si, B or P;

Y¹and Y²Each independently represents C, N, Si, B or P

Each occurrence of n is independently a valence-permitting integer;

each U, when valency permits¹And U²Represents O, S, Se, N, P, As, B, Al, Bi, P-O, As-O, Bi-O, CR²¹、CR²¹R²²、C＝O、SiR²¹、SiR²¹R²²、GeR²¹、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O or BiR²¹；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R²¹And R²²Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, or diarylaminoAlkylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof.

In one embodiment, the compound is represented by one of the following structures:

wherein each U is as defined in the specification¹And U²Independently represent N, NPh, S, O, S-O, SO₂、P＝O、Se＝O、CPh₂Or CMe₂Wherein Me is methyl and Ph is phenyl.

Compositions and devices of the invention

Also disclosed herein are organic light emitting diodes or light emitting devices comprising one or more compounds and/or compositions disclosed herein.

In one aspect, the device is an electro-optical device. Electro-optical devices include, but are not limited to, light absorbing devices such as sunlight sensitive and photosensitive devices, organic light emitting devices, or devices capable of absorbing and emitting and serving as markers for biological applications. For example, the device may be an OLED.

OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for use in, for example, flat panel displays, lighting, and backlighting applications. Several OLED materials and configurations are described in U.S. patent nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes into the organic layer, and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and a hole are located on the same molecule, an "exciton," which is a localized electron-hole pair with an excited energy state, is formed. When the exciton relaxes via a photoemissive mechanism, light is emitted. In some cases, excitons may localize to an excimer (eximer) or exciplex. Non-radiative mechanisms (e.g., thermal relaxation) may also occur, but are generally considered undesirable.

The initial OLEDs utilized emissive molecules to emit light from their singlet state ("fluorescence"), as disclosed, for example, in U.S. patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from the triplet state ("phosphorescence") have been demonstrated. Baldo et al, "Organic Electroluminescent Devices emitting phosphorescence with high efficiency" (Nature), Vol.395, 151-; ("Baldo-I") and Baldo et al, "Very high efficiency green organic electroluminescent device based on electro-phosphorescence" (Very high-efficiency green organic light-emitting devices), applied Physics journal (appl. Phys. Lett.), Vol.75, No. 3, No. 4-6 (1999) ("Baldo-II"), which are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, which is incorporated by reference.

One application of phosphorescent emissive molecules is in full color displays. Industry standards for such displays require pixels adapted to emit a particular color, known as a "saturated" color. In particular, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates well known in the art. Disclosed herein are such devices comprising one or more of the compounds or compositions disclosed herein.

OLEDs can be manufactured by methods known to those skilled in the art. Generally, OLEDs are fabricated by sequential vapor deposition of individual layers onto a suitable substrate. Suitable substrates include, for example, glass, inorganic materials (e.g., ITO or IZO), or polymer films. For vapor deposition, conventional techniques such as thermal evaporation, Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), and the like may be used.

In an alternative process, the organic layer may be coated from a solution or dispersion in a suitable solvent, in which case coating techniques known to those skilled in the art are used. Suitable coating techniques are, for example, spin coating, casting, Langmuir-Blodgett ("LB") processes, ink-jet printing, dipping, letterpress printing, screen printing, doctor blade printing, slot coating, roller printing, reverse roller printing, lithography, flexography, rotogravure, spraying, brushing or pad printing, etc. Among the processes mentioned, in addition to the aforementioned vapor deposition, spin coating, inkjet printing and casting methods are preferred, since they are particularly simple and inexpensive to carry out. In the case where each layer of the OLED is obtained by a spin coating method, a casting method, or an inkjet printing method, the coating layer may be obtained using a solution prepared by dissolving the composition in a suitable organic solvent (e.g., benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide, water, and a mixture thereof) at a concentration of 0.0001 to 90 wt%.

The compounds described herein can be used in light emitting devices (e.g., OLEDs). Fig. 1 depicts a cross-sectional view of an OLED 100. The OLED 100 includes a substrate 102, an anode 104, a hole transport material (HTL)106, a photo-processing material 108, an electron transport material (ETL)110, and a metallic cathode layer 112. The anode 104 is typically a transparent material, such as indium tin oxide. The light management material 108 may be an Emissive Material (EML) that includes an emitter and a host.

In various aspects, any of the one or more layers depicted in fig. 1 may comprise Indium Tin Oxide (ITO), poly (3, 4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), N ' -di-1-naphthyl-N, N-diphenyl-1, 1' -biphenyl-4, 4' -diamine (NPD), 1-bis ((di-4-tolylamino) phenyl) cyclohexane (TAPC), 2, 6-bis (N-carbazolyl) pyridine (mCpy), 2, 8-bis (diphenylphosphoryl) dibenzothiophene (PO15), LiF, Al, or a combination thereof.

The light management material 108 may include one or more compounds of the present disclosure, optionally together with a host material. The host material may be any suitable host material known in the art. The emission color of the OLED is determined by the emission energy (optical bandgap) of the light management material 108, which can be tuned by adjusting the electronic structure of the emissive compound, the host material, or both. Both the hole transport material in the HTL layer 106 and the electron transport material in the ETL layer 110 may include any suitable hole transporter known in the art.

The compounds described herein may exhibit phosphorescence. The device efficiency of phosphorescent OLEDs (i.e., OLEDs having phosphorescent emitters) is generally higher than that of other OLEDs, such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in more detail in WO 2000/070655 to Baldo et al, the teachings of which are incorporated herein by reference with respect to OLEDs and particularly phosphorescent OLEDs.

As contemplated herein, the OLED of the present invention may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The organic layer may comprise the compounds of the present invention and variations thereof as described herein.

In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer containing a delayed fluorescence emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is a lighting panel.

In one embodiment, the consumer product is selected from the group consisting of: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior lighting and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, a tablet computer, a phablet, a Personal Digital Assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay with a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall containing multiple displays tiled together, a theater or stadium screen, and a sign.

In some embodiments of the emission area, the emission area further comprises a body, wherein the body comprises at least one selected from the group consisting of: metal complexes, triphenylenes, carbazoles, dibenzothiophenes, dibenzofurans, dibenzoselenophenes, aza-triphenylenes, aza-carbazoles, aza-dibenzothiophenes, aza-dibenzofurans, and aza-dibenzoselenophenes.

The organic layer may further include a host. In some embodiments, two or more bodies are preferred. In some embodiments, the host used may be a) a bipolar, b) electron transport, c) hole transport, or d) a wide band gap material that plays a minor role in charge transport. In some embodiments, the body may include a metal complex. The host may be triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the subject may be a non-fused substituent independently selected from the group consisting of: CnH2N +1, OCnH2N +1, OAr1, N (CnH2N +1)2, N (Ar1) (Ar2), CH ═ CH-CnH2N +1, C ≡ C-CnH2N +1, Ar1, Ar1-Ar2, and CnH2N-Ar1, or the host has no substitution. In the foregoing substituents, n may vary from 1 to 10; and Ar1 and Ar2 may be independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host may be an inorganic compound. For example, Zn-containing inorganic materials such as ZnS.

Suitable hosts may include, but are not limited to, mCP (1, 3-bis (carbazol-9-yl) benzene), mCPy (2, 6-bis (N-carbazolyl) pyridine), TCP (1,3, 5-tris (carbazol-9-yl) benzene), TCTA (4,4',4 ″ -tris (carbazol-9-yl) triphenylamine), TPBi (1,3, 5-tris (1-phenyl-1-H-benzimidazol-2-yl) benzene), mCBP (3, 3-bis (9H-carbazol-9-yl) biphenyl), pCBP (4,4' -bis (carbazol-9-yl) biphenyl), CDBP (4,4 '-bis (9-carbazolyl) -2,2' -dimethylbiphenyl), DMFL-CBP (4,4 '-bis (carbazol-9-yl) -9, 9-dimethylfluorene), FL-4CBP (4,4' -bis (carbazol-9-yl) -9, 9-bis (9-phenyl-9H-carbazole) fluorene), FL-2CBP (9, 9-bis (4-carbazol-9-yl) phenyl) fluorene (also abbreviated as CPF), DPFL-CBP (4,4 '-bis (carbazol-9-yl) -9, 9-xylylfluorene), FL-2CBP (9, 9-bis (9-phenyl-9H-carbazole) fluorene), Spiro-CBP (2,2',7,7 '-tetrakis (carbazol-9-yl) -9,9' -spirobifluorene), ADN (9, 10-bis (naphthalen-2-yl) anthracene), TBADN (3-tert-butyl-9, 10-bis (naphthalen-2-yl) anthracene), DPVBi (4,4 '-bis (2, 2-diphenylethen-1-yl) -4,4' -dimethylphenyl), p-DMDPVBi (4,4 '-bis (2, 2-diphenylethen-1-yl) -4,4' -dimethylphenyl), TDAF (tert-9, 9-diarylfluorene)), BSBF (2- (9,9 '-spirobifluoren-2-yl) -9,9' -spirobifluorene), TSBF (2, 7-bis (9,9 '-spirobifluoren-2-yl) -9,9' -spirobifluorene), BDAF (bis (9, 9-diarylfluorene)), p-TDPVBi (4,4 '-bis (2, 2-diphenylethen-1-yl) -4,4' -di- (tert-butyl) phenyl), TPB3(1,3, 5-tris (pyrene-1-yl) benzene, PBD (2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole), BCP (2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), BP-OXD-Bpy (6,6 '-bis [5- (biphenyl-4-yl) -1,3, 4-oxadiazol-2-yl ] -2,2' -bipyridyl), NTAZ (4- (naphthalen-1-yl) -3, 5-diphenyl-4H-1, 2, 4-triazole), Bpy-OXD (1, 3-bis [2- (2,2 '-bipyridin-6-yl) -1,3,4 oxadiazol-5-yl ] benzene), BPhen (4, 7-diphenyl-1, 10-phenanthroline), TAZ (3- (4-biphenyl) -4-phenyl-5-tert-butylphenyl-1, 2, 4-triazole), PADN (2-phenyl-9, 10-bis (naphthalen-2-yl) anthracene), Bpy-FOXD (2, 7-bis [2- (2,2' -bipyridin-6-yl) -1,3, 4-oxadiazol-5-yl ] -9, 9-dimethylfluorene), OXD-7(1, 3-bis [2- (4-tert-butylphenyl) -1,3, 4-oxadiazol-5-yl ] benzene), HNBphen (2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline), NBphen (2, 9-bis (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline), 3TPYMB (tris (2,4, 6-trimethyl-3- (pyridin-3-yl) phenyl) borane), 2-NPIP (1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4,5-f ] - [1,10] phenanthroline), Liq (lithium 8-hydroxyquinoline), and Alq (bis (2-methyl-8-quinoline) -4- (phenylphenol) aluminum), as well as mixtures of the foregoing.

Materials described herein as useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the light emitting dopants disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that can be used in combination.

The charge transport layer may be doped with a conductivity dopant to substantially change its charge carrier density, which in turn will change its conductivity. The conductivity is increased by generating charge carriers in the host material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductivity dopant and an n-type conductivity dopant is used in the electron transport layer.

Non-limiting examples of conductivity dopants that can be used in OLEDs in combination with the materials disclosed herein are illustrated below and in references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US 2012146012.

Hole injection/transport for use in the present inventionThe hole injecting/transporting material is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; an aromatic amine derivative; indolocarbazole derivatives; a fluorocarbon-containing polymer; a polymer having a conductive dopant; conductive polymers such as PEDOT/PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives, e.g. MoO_x(ii) a p-type semiconducting organic compounds, such as 1,4,5,8,9, 12-hexaazatriphenylhexacyano-nitrile; a metal complex; and a crosslinkable compound.

An Electron Blocking Layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a barrier layer in the device may result in a significant increase in efficiency and/or a longer lifetime compared to a similar device lacking a barrier layer. In addition, blocking layers can be used to limit the emission to the desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the one or more bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria are met.

One or more other emitter dopants may be used in combination with the disclosed compounds. Examples of the other emitter dopant are not particularly limited, and any compound may be used as long as the compound is generally used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

A Hole Blocking Layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of the barrier layer in the device may substantially improve efficiency and/or prolong lifetime compared to a similar device lacking the barrier layer. In addition, blocking layers can be used to limit the emission to the desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than the host or hosts closest to the HBL interface.

The Electron Transport Layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used to transport electrons.

In tandem or stacked OLEDs, CGL plays an important role in performance, consisting of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and the anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer.

In any of the above compounds used in each layer of an OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically listed substituents, such as (without limitation) methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as (without limitation) alkyl, aryl, cycloalkyl, heteroaryl, and the like) can also be non-deuterated, partially deuterated, and fully deuterated forms thereof.

In yet another aspect of the present disclosure, a formulation is described comprising the novel compounds disclosed herein. The formulation may include one or more of the components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, and an electron transport layer material.

Experimental examples

The present invention is described in further detail with reference to the following experimental examples. These examples are provided for illustrative purposes only and are not intended to be limiting unless otherwise specified. Thus, the present invention should in no way be construed as being limited to the following examples in any way, but rather should be construed to cover any and all variations which become evident as a result of the teachings provided herein.

Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the composite materials of the present invention and practice the claimed methods. The following working examples therefore point specifically to preferred embodiments of the invention and are not to be construed as limiting in any way the remainder of the disclosure.

Example 1: metal-assisted delayed fluorescence

In the present invention, a series of novel donor-acceptor type potential functional materials are designed based on stable chemical structures. The material may be used as a TADF material and may be used as a hole and electron/hole blocking material, and the like. These materials can have good operational stability.

In one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

in one embodiment, exemplary compounds may be prepared according to the following scheme:

the disclosures of each patent, patent application, and publication cited herein are hereby incorporated by reference in their entirety. While the invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of the invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. It is intended that the following claims be interpreted to embrace all such embodiments and equivalent variations.

Claims (20)

1. A compound of the general formula I,

wherein:

T²and T³Represents a donor or an acceptor; t is¹Optionally represents a donor;

Y¹and Y²Each independently represents C, N, Si, B or P;

wherein when Y is¹And Y²When both represent C, then two radicals R¹May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

wherein if any two adjacent X^aAnd X^bRepresents X⁵-X⁸Wherein a and b are integers from 5 to 8, then two radicals R²May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

wherein if any two adjacent X^cAnd X^dRepresents X⁹-X¹²Where c and d are integers from 9 to 12, then two radicals R³May optionally be joined together to form a fused aryl or heteroaryl ring having the structure:

wherein:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹、X¹²、X¹³、X¹⁴、X¹⁵and X¹⁶Each independently represents C, N, Si, B or P;

U¹represents O, S, Se, NR²¹、P＝O、As＝O、Bi＝O、CR²¹R²²、C＝O、SiR²¹R²²、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O, or BiR²¹；

Each n is independently a valence-allowed integer; and is

R¹、R²、R³、R⁴、R⁵、R²¹And R²²Each independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof;

wherein two adjacent radicals R¹、R²、R³、R⁴、R⁵、R²¹、R²²Or combinations thereof may optionally be joined together to form fused rings.

2. The compound of claim 1, wherein one or more of the following conditions holds:

(i)Y¹and Y²Each is C, and two radicals R¹Represented by one of the following structures, wherein the dotted line represents Y into formula I¹And Y²The bond of (a):

(ii) for two adjacent X^aAnd X^bBy two radicals R²Represented by one of the following structures, wherein the dotted line represents X attached to formula I^aAnd X^bThe bond of (a):

or

(iii) For two adjacent X^cAnd X^dBy two radicals R³Represented by one of the following structures, wherein the dotted line represents X attached to formula I^cAnd X^dThe bond of (a):

wherein:

X¹³、X¹⁴、X¹⁵、X¹⁶、X¹⁷、X¹⁸、X¹⁹and X²⁰Each independently represents C, N, Si, B or P;

each U¹And U²Representations O, S, Se,P＝O、As＝O、Bi＝O、CR²¹R²²、C＝O、SiR²¹R²²、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O, or BiR²¹；

Each R⁴、R⁵、R⁶And R⁷Independently absent or present as a single substituent or multiple substituents, where valency permits, and R⁴、R⁵、R⁶、R²¹And R²²Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof;

any two adjacent R⁴、R⁵、R⁶、R⁷Or combinations thereof may optionally be joined together to form fused rings; and is

Each occurrence of n is independently a valence-permitting integer.

3. The compound of claim 1, wherein one or more of the following conditions holds:

(i)Y¹and Y²At least one of (A) represents C, and at least one R represents¹Represented by the following structure:

(ii) at least one R²Represented by the following structure:

or

(iii) At least one R³Represented by the following structure:

wherein

The dotted line represents a bond to formula I;

X¹³、X¹⁴、X¹⁵、X¹⁶、X¹⁷、X¹⁸、X¹⁹and X²⁰Each independently represents C, N, Si, B or P;

U¹represents N, P, As, B, Al, or Bi, CR²¹、SiR²¹、GeR²¹、P＝O、As＝O、B、Bi＝O、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、R²¹Bi ═ O, or BiR²¹；

Each R⁴、R⁵And R⁶Independently absent or present as a single substituent or multiple substituents, where valency permits, and R⁴、R⁵、R⁶、R²¹And R²²Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkylOxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymers; or any conjugate or combination thereof;

any two adjacent R⁴、R⁵、R⁶Or combinations thereof may be optionally joined to form fused rings; and is

Each occurrence of n is independently a valence-permitting integer.

4. The compound of claim 1, wherein X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹And X¹²Represents N.

5. The compound of claim 1, wherein X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹And X¹²Represents N.

6. The compound of claim 1, wherein X⁵、X⁶、X⁷And X⁸At least one of them represents N, and X⁹、X¹⁰、X¹¹And X¹²Represents N.

7. The compound of claim 1, wherein the compound is represented by formula II, formula III, formula IV, formula V, or formula VI:

wherein X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹And X¹²Each independently represents C, N, Si, B or P;

Y¹and Y²Each independently represents C, N, Si, B or P;

each occurrence of n is independently a valence-permitting integer; and is

R¹、R²And R³Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof; and is

Any two adjacent R¹、R²、R³Or combinations thereof may optionally be joined together to form fused rings.

8. The compound of claim 1, wherein the compound is represented by one of the following structures:

wherein X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、X¹¹、X¹²、X¹³、X¹⁴、X¹⁵、X¹⁶、X¹⁷、X¹⁸、X¹⁹、X²⁰、X²¹、X²²、X²³、X²⁴、X²⁵、X²⁶、X²⁷And X²⁸Each independently represents C, N, Si, B or P;

Y¹and Y²Each independently represents C, N, Si, B or P

Each occurrence of n is independently a valence-permitting integer;

each U, when valency permits¹And U²Represents O, S, Se, N, P, As, B, Al, Bi, P-O, As-O, Bi-O, CR²¹、CR²¹R²²、C＝O、SiR²¹、SiR²¹R²²、GeR²¹、GeR²¹R²²、NR²¹、PR²¹、PR²¹R²²、R²¹P＝O、AsR²¹、R²¹As＝O、S＝O、SO₂、Se＝O、SeO₂、BR²¹、BR²¹R²²、AlR²¹、AlR²¹R²²、R²¹Bi ═ O, or BiR²¹；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R²¹And R²²Each occurrence of (a) independently represents hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylaminoAlkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymer; or any conjugate or combination thereof.

9. The compound of claim 1, wherein the compound is represented by one of the following structures:

wherein each U is as defined in the specification¹And U²Independently represent N, NPh, S, O, S-O, SO₂、P＝O、Se＝O、CPh₂Or CMe₂Wherein Me is methyl and Ph is phenyl.

10. An organic light emitting diode comprising the compound of claim 1.

11. A light emitting device comprising the organic light emitting diode of claim 10.

12. An organic light emitting diode comprising the compound of claim 2.

13. A light emitting device comprising the organic light emitting diode of claim 12.

14. An organic light emitting diode comprising the compound of claim 3.

15. An organic light emitting diode comprising the compound of claim 7.

16. A light emitting device comprising the organic light emitting diode of claim 15.

17. An organic light emitting diode comprising the compound of claim 8.

18. A light emitting device comprising the organic light emitting diode of claim 17.

19. An organic light emitting diode comprising the compound of claim 9.

20. A light emitting device comprising the organic light emitting diode of claim 19.

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