Organic compound containing seven-membered nitrogen heterocycle and use thereof in organic electronic devices

Abstract

The present application relates to a kind of containing seven-membered nitrogen heterocyclic organic compound, seven-membered nitrogen heterocycle has good electron-donating ability;With terminal electron-withdrawing group A connection, make it have good charge mobility and appropriate energy level and have good chemical stability, as small molecule acceptor material is applied in organic solar cell, to improve the photoelectric conversion efficiency of device.

Description

Technical Field

[0001] This invention relates to the field of organic solar cell materials, and in particular to a seven-membered nitrogen heterocyclic organic compound and its application in organic electronic devices. Background Technology

[0002] Organic solar cells (OPVs) have garnered significant global attention due to their low cost, lightweight nature, simple fabrication process, and ability to be flexibly fabricated over large areas. An OPV typically consists of five parts: an anode, an anode buffer layer, an active layer, a cathode buffer layer, and a cathode. The active layer generally contains donor and acceptor materials. The working principle of an OPV is as follows: When sunlight passes through a transparent substrate and electrodes and strikes the active layer, the donor and acceptor materials absorb photons with energy exceeding their band gaps. Electrons are excited from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), simultaneously creating corresponding holes at the HOMO. Because organic materials have a relatively low permittivity, the electrons and holes exist as bound excitons. These excitons then diffuse to the donor-acceptor interface, where, driven by the energy level difference, they dissociate, achieving charge separation. Subsequently, under the influence of a built-in electric field, the free holes and electrons travel along continuous channels in the donor and acceptor materials to the anode and cathode, respectively, where they are collected by the electrodes and output to the external circuit to form a current. Therefore, the choice of active layer material is crucial to the efficiency of organic solar cell devices.

[0003] In the early to mid-stages of organic solar cell development, fullerenes and their derivatives, represented by PC61BM and PC71BM, dominated the electron acceptor materials due to their high electron affinity, isotropic electron transport capabilities, and high electron mobility. This period is often referred to as the fullerene era. However, the limitations of the fullerene acceptor molecular structure resulted in weak absorption in the visible light region and poor energy level tunability, restricting the efficiency improvement of organic solar cells. In recent years, the emergence of non-fullerene acceptor materials has overcome the shortcomings of fullerene acceptors to some extent, greatly improving the photoelectric conversion efficiency of devices and promoting the development of the organic solar cell field. Most existing non-fullerene acceptor materials adopt large fused ring cores, such as ITIC and Y6 structures. Although they exhibit excellent device performance, their complex structure synthesis, long synthesis routes, low reaction yields, and high synthesis costs severely limit the industrialization of organic solar cells.

[0004] Therefore, it is necessary to develop new, high-efficiency, and easily synthesized non-fullerene acceptor materials for organic solar cells to promote the industrialization of organic solar cells. Summary of the Invention

[0005] The purpose of this invention is to provide a novel non-fused-ring acceptor organic compound with a seven-membered nitrogen heterocycle as its core. Its synthesis is simple and it can be used as a small molecule acceptor material in organic solar cells, which can help improve the photoelectric conversion efficiency of the device.

[0006] To achieve the objective of this invention, the technical solution is as follows:

[0007] A seven-membered nitrogen heterocyclic organic compound having the structure shown in general formula (I):

[0008]

[0009] in,

[0010] Ar1 and Ar2 are independently selected from structural formulas (A-1), (A-2), (A-3), and (A-4), or combinations thereof:

[0011]

[0012] Among them, W is selected from O, S, and CR. 11 R 12 or NR 13 ;

[0013] R0-R 13 Each occurrence is independently selected from: -H, -D, straight-chain alkyl groups having 1 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, straight-chain alkylthio groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, branched or cyclic alkoxy groups having 3 to 20 carbon atoms, branched or cyclic alkylthio groups having 3 to 20 carbon atoms, silyl groups, ketone groups having 1 to 20 carbon atoms, and groups having 2 to 2 carbon atoms. An alkoxycarbonyl group with 0 carbon atoms, an aryloxycarbonyl group with 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a halocarbamoyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amino group, a -Cl group, a -Br group, a -F group, a -I group, a substituted or unsubstituted aromatic group with 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group with 5 to 10 ring atoms, or a group formed by a combination of the above groups;

[0014] * indicates a connection point;

[0015] EG1 and EG2 are independently selected from electron-withdrawing groups.

[0016] Accordingly, the present invention also provides a mixture comprising the above-mentioned seven-membered nitrogen heterocyclic organic compound and at least one organic functional material, wherein the organic functional material is selected from anodic buffer layer material, cathode buffer layer material, active layer donor material, or active layer acceptor material.

[0017] Accordingly, the present invention also provides an electron acceptor material, wherein the electron acceptor material is selected from the above-mentioned seven-membered nitrogen heterocyclic organic compounds or mixtures thereof.

[0018] Accordingly, the present invention also provides an organic electronic device comprising at least one functional layer, wherein the material of the functional layer is selected from the above-mentioned organic compounds or mixtures containing seven-membered nitrogen heterocycles.

[0019] The significant advantages of this invention compared to existing technologies are:

[0020] This invention provides a novel non-fused-ring acceptor containing a seven-membered nitrogen heterocyclic organic compound with an A-π-D-π-A configuration, wherein the core D is selected from a seven-membered heterocycle. This seven-membered nitrogen heterocyclic group possesses good electron-donating ability; it is connected to the terminal electron-withdrawing group A through a linking unit, giving the compound good charge mobility, suitable energy levels, and good chemical stability. When used as a small molecule acceptor material in organic solar cells, it exhibits high device photoelectric conversion efficiency. Furthermore, the compound protected by this invention uses readily available raw materials, has a simple synthetic route, low preparation cost, and can be mass-produced, showing promising prospects for industrial application. Detailed Implementation

[0021] To make the objectives, technical solutions, and effects of this application clearer and more explicit, the following provides a further detailed description of this application. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0022] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

[0023] In this invention, organic photovoltaic devices, organic solar cells, and OPV have the same meaning and can be used interchangeably.

[0024] In this invention, aromatic groups, aromatic families, and aromatic ring systems have the same meaning and can be used interchangeably.

[0025] In this invention, heteroaromatic groups, heteroaromatic families, and heteroaromatic ring systems have the same meaning and can be used interchangeably.

[0026] In this invention, "heteroatoms" are non-carbon atoms, and can be N atoms, O atoms, S atoms, etc.

[0027] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0028] In this invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

[0029] In this invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that the defined group can be substituted by one or more substituents R, wherein R is selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-20 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl, trifluoromethyl, and the above groups may also be further substituted by substituents acceptable in the art; it is understood that R' and R" in -NR'R" are each independently selected from, but not limited to: H, deuterium The group R is selected from, but is not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 carbon atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms. Preferably, R is selected from, but is not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 carbon atoms, heterocyclic group containing 3-10 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl, trifluoromethyl, and the above groups may be further substituted with substituents acceptable in the art.

[0030] In this invention, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., monocyclic compound, fused-ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, the benzene ring has 6 ring atoms, the naphthalene ring has 10 ring atoms, and the thiophene group has 5 ring atoms.

[0031] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6 to 40 ring atoms" means an aryl containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl having 6 to 14 ring atoms, and optionally further substituted on the aryl group; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl and their derivatives. Understandably, multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N, or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, and diaryl ether systems should also be included in the definition of aryl.

[0032] "Heteroaryl or heteroaromatic group" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc. For example, "substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms" refers to a heteroaryl group having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl group having 6 to 14 ring atoms. The heteroaryl group may optionally be further substituted, and suitable examples include, but are not limited to: thiophene, furanyl, pyrrole, diazolyl, triazolyl, imidazole, pyridyl, bipyridyl, pyrimidinyl, etc. Triazinyl, acridineyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidineyl, pyridinylpyrazinyl, benzothiopheneyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrololyl, thienopyrrololyl, thienopyrrololyl, furanolololyl, furanolofuranyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridineyl, primidyl, quinazolinoneyl, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl and their derivatives.

[0033] In this invention, "alkyl" can refer to a straight-chain, branched, and / or cyclic alkyl group. The number of carbon atoms in an alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 15, or 1 to 6. Phrases containing this term, such as "C1-9 alkyl," refer to alkyl groups containing 1 to 9 carbon atoms, and each occurrence can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyl 2-Hexyldecyl, 2-Octylide, n-Undecyl, n-Dodecyl, 2-Ethyldodecyl, 2-Butyldodecyl, 2-Hexyldodecyl, 2-Octylide, n-Tridecyl, n-Tetradecyl, n-Pentadedecyl, n-Hexadecyl, 2-Ethylhexadecyl, 2-Butylhexadecyl, 2-Hexylhexadecyl, 2-Octylide, n-Heptadedecyl, n-Octadedecyl, n-Nondecyl, n-Eicosyl, 2-Ethyleicosyl, 2-Butyleicosyl, 2-Hexyleicosyl, 2-Octylide, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, etc.

[0034] "Amino group" refers to a derivative of an amine, possessing the structural characteristic of the formula -N(X)2, where each "X" is independently H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, etc. Non-limiting types of amino groups include -NH2, -N(alkyl)2, -NH(alkyl), -N(cycloalkyl)2, -NH(cycloalkyl), -N(heterocyclic)2, -NH(heterocyclic), -N(aryl)2, -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclic), -N(cycloalkyl)(heterocyclic), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0035] In this invention, unless otherwise defined, hydroxyl refers to -OH, carboxyl refers to -COOH, carbonyl refers to -C(=O)-, amino refers to -NH2, formyl refers to -C(=O)H, haloformyl refers to -C(=O)z (where z represents halogen), carbamoyl refers to -C(=O)NH2, isocyanate refers to -NCO, and isothiocyanate refers to -NCS.

[0036] The term "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to another group via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu). The term "alkathio" refers to a group with the structure "-S-alkyl", that is, an alkyl group as defined above that is attached to another group via a sulfur atom.

[0037] In this invention, "*" represents a connection or fusion site.

[0038] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0039] In this invention, when the same group contains multiple substituents with the same symbol, the substituents can be the same as or different from each other, for example... The six R's on the benzene ring can be the same or different from each other.

[0040] In this invention, the phrase "independently selected" means that when one or more groups appear simultaneously and in multiple places in the compound, they are all independently selected and can be the same or different.

[0041] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0042] The terms “combinations thereof,” “any combination thereof,” “any combination thereof,” and “combination” used in this invention include all suitable combinations of any two, any three, or any three or more items of the listed groups.

[0043] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0044] In this invention, "optionally," "optionally," and "optional" mean that they are optional, that is, they are selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent.

[0045] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0046] In this invention, electron-donating groups are groups or atoms with a stronger electron-donating ability than hydrogen, i.e., they exhibit an electron-donating inductive effect; while electron-withdrawing groups are groups or atoms with a stronger electron-withdrawing ability than hydrogen, i.e., they exhibit an electron-withdrawing inductive effect. The inductive effect is the effect of the bonding electron cloud shifting in a certain direction along the atomic bond due to the difference in polarity (electronegativity) of atoms or groups in the molecule. The electron cloud shifts towards the group or atom with stronger electronegativity.

[0047] To achieve the objectives of this invention, the specific technical solution is as follows:

[0048] A seven-membered nitrogen heterocyclic organic compound having the structure shown in general formula (I):

[0049]

[0050] in,

[0051] Ar1 and Ar2 are independently selected from structural formulas (A-1), (A-2), (A-3), and (A-4), or combinations thereof:

[0052]

[0053] in,

[0054] W is selected from O, S, CR 11 R 12 or NR 13 ;

[0055] R0-R 13Each is independently selected from: -H, -D, straight-chain alkyl groups having 1 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, straight-chain alkylthio groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, branched or cyclic alkoxy groups having 3 to 20 carbon atoms, branched or cyclic alkylthio groups having 3 to 20 carbon atoms, silyl groups, ketone groups having 1 to 20 carbon atoms, and alkoxycarbonyl groups having 2 to 20 carbon atoms. The group comprises aryloxycarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms, or groups formed by combinations of the above groups; wherein one or more H atoms in the above groups are unsubstituted or substituted with deuterium;

[0056] * indicates a connection point;

[0057] EG1 and EG2 are independently selected from electron-withdrawing groups.

[0058] EG1 and EG2 have a strong electron-withdrawing effect. Located at the two ends of an organic compound, they enable the organic compound to have strong visible light absorption, high charge transport performance, and suitable electronic energy levels.

[0059] In one embodiment, the seven-membered nitrogen-containing heterocyclic organic compound is selected from general formula (II-1), general formula (II-2), general formula (II-3) or general formula (II-4):

[0060]

[0061] In one embodiment, Independently selected from any of the following groups:

[0062]

[0063] in:

[0064] Each time M appears, it is independently selected from O, S, or C(CN)2;

[0065] Each time X appears, it is independently selected from CR. 14 Or N;

[0066] Each time Y appears, it is independently selected from O, S, or Se;

[0067] R 14 R 15Each occurrence is independently selected from: -H, -D, straight-chain alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 3 to 8 carbon atoms, cyano, nitro, -Cl, -Br, -F, -I, or groups formed by combinations of the above groups; any two adjacent R groups 14 They may form rings or not;

[0068] * indicates a connection point.

[0069] In one embodiment, the "arbitrary two adjacent R" 14 "Interlocking" preferably forms a ring around R * Substituted or unsubstituted five-membered heteroaryl rings, or those modified by R * Substituted or unsubstituted six-membered aromatic groups or heteroaromatic groups; said R * Each occurrence is independently selected from: -D, a straight-chain alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cyano group, a nitro group, -Cl, -Br, -F, -I, or a group formed by a combination of the above groups. In one embodiment, the "arbitrary two adjacent R" refers to... 14 "Interlocking" preferably forms a ring around R * Substituted or unsubstituted six-membered benzene ring, or R * Substituted or unsubstituted five-membered thiophene ring.

[0070] In one embodiment, each occurrence of Y is independently selected from S.

[0071] In one embodiment, Independently selected from the following groups:

[0072]

[0073] Where: R 14 Each occurrence is independently selected from -H, -D, straight-chain alkyl with 1 to 6 carbon atoms, branched alkyl with 3 to 6 carbon atoms, cyano, nitro, -Cl, -Br, -F, -I, or a group formed by a combination of the above groups;

[0074] R 15 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 6 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms.

[0075] Furthermore, R 14 Each occurrence is independently selected from -H, -D, methyl, ethyl, propyl, isopropyl, tert-butyl, -Cl, -Br, -F, -I, -CN, -NO2, or -CF3.

[0076] In one embodiment, Independently selected from the following groups:

[0077]

[0078]

[0079]

[0080] In one embodiment, Selected from the same group.

[0081] In one embodiment, R0 is selected from: -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups; one or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0082] In one embodiment, R0 is selected from straight-chain alkyl groups having 1 to 15 C atoms, or branched or cyclic alkyl groups having 3 to 15 C atoms; one or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0083] In one embodiment, R0 is selected from methyl, ethyl, straight-chain or branched C3H7, straight-chain or branched C4H9, straight-chain or branched C5H 11 Straight or branched C6H 13 Straight or branched C7H 15 Straight or branched C8H 17 Straight or branched C9H 19 Straight or branched C 10 H 21 Straight or branched C 11 H 23 Straight or branched C 12 H 25 Straight or branched C 13 H 27 Straight or branched C 14 H 29 Straight or branched C 15 H 31 One or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0084] In one embodiment, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13The group is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups.

[0085] In one embodiment, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 The group is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 15 carbon atoms, a straight-chain alkoxy group having 1 to 15 carbon atoms, a straight-chain alkylthio group having 1 to 15 carbon atoms, a branched or cyclic alkyl group having 3 to 15 carbon atoms, a branched or cyclic alkoxy group having 3 to 15 carbon atoms, a branched or cyclic alkylthio group having 3 to 15 carbon atoms, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups.

[0086] In one embodiment, R1-R2 are independently selected from -H, -D, straight-chain alkyl groups having 1 to 15 C atoms, branched alkyl groups having 3 to 15 C atoms, or groups formed by combinations of the above groups.

[0087] Furthermore, general formula (II-2) is selected from the following general formula:

[0088]

[0089] R1 is independently selected from -H, -D, straight-chain alkyl groups having 1 to 15 C atoms, branched alkyl groups having 3 to 15 C atoms, or groups formed by combinations of the above groups.

[0090] In one embodiment, R1 in general formula (III-1) is independently selected from -H, -D, methyl, ethyl, straight-chain or branched C3H7, straight-chain or branched C4H9, straight-chain or branched C5H 11 Straight or branched C6H 13 Straight or branched C7H 15 Straight or branched C8H 17 Straight or branched C9H 19 Straight or branched C 10 H 21 Straight or branched C 11 H 23 Straight or branched C12 H 25 Straight or branched C 13 H 27 Straight or branched C 14 H 29 Straight or branched C 15 H 31 One or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0091] In one embodiment, R1 in general formula (III-1) is independently selected from -H, -D, straight-chain alkyl having 1 to 10 C atoms, or branched alkyl having 1 to 10 C atoms.

[0092] In one embodiment, R3-R4 are independently selected from -H, -D, straight-chain alkyl groups having 1 to 15 C atoms, branched alkyl groups having 3 to 15 C atoms, or groups formed by combinations of the above groups.

[0093] Furthermore, general formula (II-3) is selected from the following general formula:

[0094]

[0095] R4 is independently selected from -H, -D, straight-chain alkyl groups having 1 to 15 carbon atoms, branched alkyl groups having 3 to 15 carbon atoms, or groups formed by combinations of the above groups.

[0096] In one embodiment, R4 is independently selected from -H, -D, methyl, ethyl, straight-chain or branched C3H7, straight-chain or branched C4H9, straight-chain or branched C5H 11 Straight or branched C6H 13 Straight or branched C7H 15 Straight or branched C8H 17 Straight or branched C9H 19 Straight or branched C 10 H 21 Straight or branched C 11 H 23 Straight or branched C 12 H 25 Straight or branched C 13 H 27 Straight or branched C 14 H 29 Straight or branched C 15 H 31 One or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0097] In one embodiment, R4 in general formula (III-2) is independently selected from -H, -D, straight-chain alkyl having 1 to 10 C atoms, or branched alkyl having 1 to 10 C atoms.

[0098] In one embodiment, R5-R8 are independently selected from -H, -D, straight-chain alkyl groups having 1 to 15 C atoms, branched alkyl groups having 3 to 15 C atoms, aromatic groups having 6 to 10 cyclic atoms, or groups formed by combinations of the above groups.

[0099] Furthermore, R5-R6 are selected from -H.

[0100] In one embodiment, R7-R8 are selected from -H, -D, straight-chain alkyl groups having 1 to 10 C atoms, branched alkyl groups having 3 to 10 C atoms, aromatic groups having 6 to 10 cyclic atoms, or groups formed by combinations of the above groups.

[0101] In one embodiment, R7-R8 are selected from straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, and groups treated with R... # The R is a substituted or unsubstituted phenyl group. # It is selected from straight-chain alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms.

[0102] In one embodiment, R9-R 10 It is independently selected from -H, -D, straight-chain alkyl groups having 1 to 10 carbon atoms, and branched alkyl groups having 3 to 10 carbon atoms.

[0103] In one embodiment, R9-R 10 Selected from -H.

[0104] In one embodiment, R 11 R 12 R 13 A group independently selected from -H, -D, straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, or combinations thereof. Further, R 13 Selected from -H, -D, and straight-chain alkyl groups having 1 to 10 carbon atoms. R 11- R 12 It is selected from -H, -D, straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, or groups formed by combinations of the above groups.

[0105] In one embodiment, R 11 R 12 R 13 Independently selected from methyl, ethyl, straight-chain or branched C3H7, straight-chain or branched C4H9, straight-chain or branched C5H 11 Straight or branched C6H 13 Straight or branched C7H 15 Straight or branched C8H 17Straight or branched C9H 19 Straight or branched C 10 H 21 One or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0106] In one embodiment, Ar1 and Ar2 are selected from the same group.

[0107] In one embodiment, the organic compound containing a seven-membered nitrogen heterocycle provided by the present invention is a compound with a symmetrical structure.

[0108] A specific example of a seven-membered nitrogen heterocyclic organic compound according to the present invention is as follows, but is not limited thereto:

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] The seven-membered nitrogen heterocyclic organic compound provided by the present invention can be used as an active layer material in organic electronic devices; preferably, the seven-membered nitrogen heterocyclic organic compound according to the present invention can be used as an active layer acceptor material in organic solar energy devices.

[0122] The present invention also provides a mixture comprising at least one of the seven-membered nitrogen heterocyclic organic compounds described above, and at least one other organic functional material, wherein the at least one other organic functional material may be selected as an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material. The weight ratio of the mixture to the other organic functional material is from 1:99 to 99:1. In one embodiment, the photoactive layer comprises a donor material and an acceptor material, with a weight ratio of donor material / acceptor material = 1 / 1.2.

[0123] In one embodiment, the other organic functional material is selected from active layer donor materials or active layer acceptor materials.

[0124] In one embodiment, the mixture according to the present invention comprises at least one of the organic compounds described above, and at least one other organic functional material selected from PBDB-T, PM6, PM7, PTQ10, or a combination thereof.

[0125] This application further relates to an electron acceptor material, wherein the electron acceptor material is selected from the seven-membered nitrogen heterocyclic organic compounds or mixtures described above; when the electron acceptor material is selected from a mixture, the organic mixture is selected from at least one of the seven-membered nitrogen heterocyclic organic compounds and at least another active layer acceptor material; in one embodiment, the other active layer acceptor material is selected from fullerenes and their derivatives, such as PC61BM, PC71BM and their derivatives.

[0126] This application also relates to a composition comprising at least one seven-membered nitrogen heterocyclic organic compound or mixture as described above, and at least one organic solvent. The organic solvent is selected from aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers, or mixtures thereof.

[0127] Specifically, the aforementioned organic solvents may be selected from dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,5-dimethyltetrahydrofuran, acetophenone, acetophenone, tetrahydronaphthalene, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indene, methyl benzoate, ethyl benzoate, mesitylene, or a mixture of any two or more of the aforementioned organic solvents.

[0128] In a preferred embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0129] It should be noted that the above-mentioned organic solvent can evaporate from the solvent system to form a thin film comprising the organic compound or mixture.

[0130] In some embodiments, the composition is a solution. In other embodiments, the composition is a suspension. The solution or suspension may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from, but are not limited to, at least one of surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, and adhesives.

[0131] This application also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices. In one embodiment, the composition is used to prepare organic electronic devices by a printing or coating method. The printing or coating method can be, but is not limited to, inkjet printing, gravure printing, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, slot extrusion coating, etc. Preferably, slot coating, spin coating, and inkjet printing are used.

[0132] This application further relates to the application of a seven-membered nitrogen heterocyclic organic compound, mixture, or composition as described above in organic electronic devices. The organic electronic devices may be, but are not limited to, organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes, with OPVs being particularly preferred.

[0133] This application also relates to an organic electronic device comprising at least one functional layer, wherein the functional layer contains the aforementioned seven-membered nitrogen-containing heterocyclic organic compound or a mixture thereof, or is prepared from the aforementioned composition. Preferably, the functional layer is selected from an anodic buffer layer, an active layer, or a cathode buffer layer.

[0134] In one embodiment, the organic electronic device includes at least a first electrode, a second electrode, and one or more functional layers located between the first electrode and the second electrode. Preferably, the one or more functional layers are selected from active layers; more preferably, the one or more functional layers are selected from an anode buffer layer, an active layer, and a cathode buffer layer.

[0135] It should be noted that, in order to improve the performance of organic solar cell devices, the functional layer may further include other functional layers, including but not limited to charge injection layer and / or charge blocking layer.

[0136] Furthermore, the organic solar cell also includes a substrate. Specifically, the substrate may be disposed below the first electrode.

[0137] In one embodiment, the first electrode is an anode and the second electrode is a cathode; in another embodiment, the first electrode may be a cathode and the second electrode may be an anode.

[0138] In one embodiment, a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance can be used as the substrate. Specifically, a glass substrate, a thin-film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include, but is not limited to, single-layer or multi-layer films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), and polyimide (PI), and substrates commonly used in organic solar cells may also be used.

[0139] At least one of the first and second electrodes is transparent or translucent to allow light to enter. The materials used to prepare the electrodes can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd), or their alloys; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO∶Al or SnO2∶Sb; and conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline; or materials with multilayer structures, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al∶Li, Al∶BaF2, and Al∶BaF2∶Ba, but are not limited thereto.

[0140] The active layer comprises electron donor materials and electron acceptor materials. In this specification, the active layer material may refer to both electron donor materials and electron acceptor materials.

[0141] Specifically, the electron acceptor material is selected from seven-membered nitrogen heterocyclic organic compounds or mixtures as described in this invention.

[0142] Specifically, the electron donor material can be a variety of polymer materials or small molecule materials. The polymer materials can be selected from polythiophene material systems, such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymer material systems, such as PF8BT, etc.; novel structural narrow bandgap polymer material systems, such as benzothiadiazoles (BT, BBT), quinoxalines (QU, PQ), pyrazines (TP, PQ) and copolymers with electron-rich groups (such as thiophene derivatives), such as PCDTBT, PCPDTBT, PFO-DBT, PTB7, PM6, PM7, PBDB-T, J52, PTQ10, D18, etc. Small molecule materials can be selected from one or more of the following: copper phthalocyanine (II), zinc phthalocyanine, tris[4-(5-dicyanomethylenemethyl-2-thienyl)phenyl]amine, 2,4-bis[4-(N,N-dibenzylamino)-2,6-dihydroxyphenyl]squamine, benzo[b]anthracene and pentabenzene, B8, B10, etc.

[0143] The photoactive layer can be formed by dissolving a photoactive material, such as an electron donor and / or an electron acceptor, in an organic solvent, and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spraying, doctor blade coating, slot coating, and inkjet printing, but not limited thereto.

[0144] The anode buffer layer material can be selected from poly(styrene sulfonic acid) PEDOT:PSS (poly(3,4-ethylenedioxythiophene)), molybdenum oxide (MoOx), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO4), etc. x Preferably, x is selected from 2 or 3, etc., but not limited to this.

[0145] The cathode buffer layer material can be an electron-withdrawing metal oxide or polymer. The metal oxide can be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc., and the polymer can be PFN-Br or PFN, etc., but is not limited to these.

[0146] In one embodiment, an organic electronic device according to the present invention comprises at least a first electrode, a second electrode, and one or more functional layers located between the first electrode and the second electrode. Each functional layer comprises at least a photoactive layer containing a donor material and an acceptor material. The acceptor material is selected from seven-membered nitrogen-containing heterocyclic organic compounds or mixtures as described above, and the donor material is selected from a mixture of PM6 and PTQ10. Further, the mass ratio of the donor material to the acceptor material is 1:1 to 1:1.2. Further, the mass ratio of PM6 to PTQ10 is 1:0.1 to 0.1:1. In one embodiment, the mass ratio of PM6 to PTQ10 is further 0.8:0.2. Preferably, the organic electronic device is an organic solar cell.

[0147] This invention also relates to the application of organic solar cells according to the invention in various devices, including, but not limited to, building-integrated photovoltaics (BIPV), electronic shelf labels, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0148] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0149] Examples of compounds and organic electronic devices according to the present invention are given herein, but the present invention is not limited to the following embodiments.

[0150] Compound preparation:

[0151] Example 1: Synthesis of Compound 1

[0152]

[0153] Synthesis of compound 1-1:

[0154] Compound A (58.2 g, 200 mmol) was accurately weighed and added to a 1000 mL three-necked flask. Approximately 600 mL of tetrahydrofuran was added, and the mixture was purged with nitrogen three times under purging pressure. The temperature was then lowered to approximately 0 °C. NBS solution (14 g dissolved in 150 mL of THF) was slowly added dropwise to the reaction system. After the addition was complete, the mixture was allowed to warm to room temperature and reacted overnight. After the starting material had completely reacted, the mixture was washed with water, extracted with ethyl acetate, and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove excess solvent, yielding approximately 78.3 g of crude product. Yield: 87.2%. Ms: 450.52.

[0155] Synthesis of compounds 1-2:

[0156] Compound 1-1 (44.9 g, 100 mmol), isooctane bromo (23.2 g, 120 mmol), bis(di-benzylacetone)palladium (1.7 g, 3 mmol), and sodium tert-butoxide (19.2 g, 200 mmol) were weighed and added sequentially to a 1000 mL three-necked flask. Approximately 600 mL of anhydrous toluene was added, and the mixture was purged with nitrogen three times. Then, approximately 14 mL of a toluene solution of tri-tert-butylphosphine (10% bulk ratio) was slowly added dropwise. The mixture was then slowly heated to 100 °C and reacted overnight. After the reactants had completely reacted, the mixture was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove excess solvent. The mixture was then subjected to silica gel column chromatography with PE:DCM = 10:1 (volume ratio) as the eluent, yielding approximately 41.9 g of compound 1-2, yield: 74.2%. Ms: 561.45.

[0157] Synthesis of compounds 1-3:

[0158] Accurately weigh compounds 1-2 (39.3 g, 70 mmol), pinacol diborate (39.1 g, 154 mmol), palladium dichloride bis(triphenylphosphine) (1.54 g, 2.1 mmol), and potassium acetate (20.6 g, 210 mmol) and add them sequentially to a 1000 mL three-necked flask. Add approximately 600 mL of anhydrous dioxane, purge with nitrogen three times, and then heat to 100 °C for four hours. After the starting materials have completely reacted, cool to room temperature, dilute with water, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 5:1 (v / v) to obtain approximately 34.4 g of compounds 1-3, yield: 75.1%. Ms: 655.90.

[0159] Synthesis of compounds 1-5:

[0160] Accurately weigh 59.4 g (100 mmol) of compounds 1-4 into a 2000 mL three-necked flask, add approximately 600 mL of anhydrous THF, purge with nitrogen three times, then cool to -80 °C with liquid nitrogen and ethanol. Slowly add 40 mL of 2.5 M butyllithium to the flask, maintaining the reaction at low temperature for 1 hour. Then slowly add 15.5 mL of anhydrous DMF to the reaction system, allowing it to naturally warm to room temperature and react for 4 hours. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:EA = 8:1 (v / v) as eluent to obtain approximately 42.6 g of compounds 1-5, yield: 78.5%. Ms: 542.08.

[0161] Synthesis of compounds 1-6:

[0162] Accurately weigh compounds 1-5 (42.6 g, 78.5 mmol) into a 1000 mL three-necked flask, add 500 mL of tetrahydrofuran, purge with nitrogen three times, and then cool to approximately 0 °C. Slowly add NBS (14 g dissolved in 150 mL of THF) dropwise to the reaction system. After the addition is complete, allow the mixture to warm to room temperature and react overnight. After the starting materials have completely reacted, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation to obtain approximately 43 g of crude product. Yield: 88%. Ms: 622.96.

[0163] Synthesis of compounds 1-7:

[0164] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), compounds 1-6 (37.3 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of anhydrous toluene and 100 mL of water. After purging with nitrogen three times, heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 36.3 g of compounds 1-7, yield: 81.4%. Ms: 1485.37.

[0165] Synthesis of Compound 1:

[0166] Accurately weigh compounds 1-7 (7.4 g, 5 mmol), compounds 1-8 (1.94 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.7 g of compound 1. Yield: 51.9%. Ms: 1837.84.

[0167] Example 2: Synthesis of Compound 3

[0168]

[0169] Synthesis of compound 3:

[0170] Accurately weigh compounds 1-7 (7.4 g, 5 mmol), compounds 2-1 (2.3 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 4.4 g of compound 3. Yield: 46.1%. Ms: 1909.74.

[0171] Example 3: Synthesis of Compound 4

[0172]

[0173] Synthesis of compound 3-1:

[0174] The synthetic route for compound 3-1 is the same as that for compound 1-2, except that bromoisooctane is replaced with 2-butyl-1-bromooctane, yielding approximately 44.6 g of compound 3-1, with a yield of 72.4%. Ms: 618.14.

[0175] Synthesis of compound 3-2:

[0176] The synthetic route for compound 3-2 is the same as that for compound 1-3, except that compound 1-2 is replaced with compound 3-1, yielding approximately 37.8 g of compound 3-2, with a yield of 75.6%. Ms: 712.07.

[0177] Synthesis of compounds 3-4:

[0178] Accurately weigh 44.1 g (100 mmol) of compound 3-3 into a 2000 mL three-necked flask, add approximately 600 mL of anhydrous THF, purge with nitrogen three times, then cool to -80 °C with liquid nitrogen and ethanol. Slowly add 40 mL of 2.5 M lithium to the flask, maintaining the reaction at low temperature for 1 hour. Then slowly add 15.5 mL of anhydrous DMF to the reaction system, allowing it to naturally warm to room temperature and react for 4 hours. After the starting material has completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:EA = 8:1 (v / v) as eluent to obtain approximately 31.6 g of compound 3-4, yield: 80.9%. Ms: 391.06

[0179] Synthesis of compounds 3-5:

[0180] Accurately weigh compound 3-4 (31.3 g, 80 mmol) into a 1000 mL three-necked flask, add 500 mL of tetrahydrofuran, purge with nitrogen three times, and cool to approximately 0 °C. Slowly add NBS (14 g dissolved in 150 mL of THF) dropwise to the reaction system. After the addition is complete, allow the mixture to warm to room temperature and react overnight. After the starting material has completely reacted, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation to obtain approximately 32.5 g of crude product. Yield: 86.5%. Ms: 469.85

[0181] Synthesis of compounds 3-6:

[0182] Accurately weigh compound 3-2 (21.3 g, 30 mmol), compound 3-5 (28.2 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) as eluent to obtain approximately 26.3 g of compound 3-6, yield: 70.9%. Ms: 1236.53.

[0183] Synthesis of compound 4:

[0184] Accurately weigh compounds 3-6 (6.2 g, 5 mmol), compounds 3-7 (2.63 g, 10 mmol), and pyridine (1.6 g, 20 mmol) and add them sequentially to a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the starting materials have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 3:1 (volume ratio) as the eluent to obtain approximately 4.1 g of compound 4, yield: 47.5%.

[0185] Ms: 1726.78

[0186] Example 4: Synthesis of Compound 18

[0187]

[0188] Synthesis of compound 4-2:

[0189] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), compound 4-1 (31.5 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have reacted completely, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 26.3 g of compound 4-2, yield: 67.8%. Ms: 1292.79.

[0190] Synthesis of compound 18:

[0191] Accurately weigh compound 4-2 (6.5 g, 5 mmol), compound 4-3 (1.93 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.8 g of compound 18. Yield: 46.2%. Ms: 1643.63

[0192] Example 5: Synthesis of Compound 23

[0193]

[0194] Synthesis of compound 23:

[0195] Accurately weigh compounds 3-6 (6.2 g, 5 mmol), 5-1 (1.93 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.6 g of compound 23. Yield: 44.5%. Ms: 1629.26

[0196] Example 6: Synthesis of Compound 52

[0197]

[0198] Synthesis of compound 6-2:

[0199] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 6-1 (16.5 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have reacted completely, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 18.6 g of compound 6-2, yield: 78.3%. Ms: 792.58.

[0200] Synthesis of compound 52:

[0201] Accurately weigh compound 6-2 (4.0 g, 5 mmol), compound 6-3 (2.8 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.1 g of compound 52. Yield: 47.1%. Ms: 1316.75.

[0202] Example 7: Synthesis of Compound 54

[0203]

[0204] Synthesis of compound 7-1:

[0205] Accurately weigh compound 3-2 (21.3 g, 30 mmol), compound 6-1 (16.5 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have reacted completely, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 18.6 g of compound 7-1, yield: 73.1%. Ms: 848.52.

[0206] Synthesis of compound 54:

[0207] Accurately weigh compound 7-1 (4.0 g, 5 mmol), compound 7-2 (1.8 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 2.6 g of compound 54, yield: 44%. Ms: 1176.95

[0208] Example 8: Synthesis of Compound 55

[0209]

[0210] Synthesis of compound 8-2:

[0211] Accurately weigh compound 3-2 (21.3 g, 30 mmol), compound 8-1 (11.5 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 15.6 g of compound 8-2, yield: 76.5%. Ms: 680.03.

[0212] Synthesis of compound 55:

[0213] Accurately weigh compound 8-2 (3.4 g, 5 mmol), compound 8-3 (1.95 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 2.4 g of compound 55. Yield: 46.6%. Ms: 1034.95

[0214] Example 9: Synthesis of Compound 76

[0215]

[0216] Synthesis of compound 9-2:

[0217] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), compound 9-1 (18.2 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have reacted completely, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 15.6 g of compound 9-2, yield: 63.8%. Ms: 848.70.

[0218] Synthesis of compound 76:

[0219] Accurately weigh compound 9-2 (4.24 g, 5 mmol), compound 9-3 (2.56 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 2.9 g of compound 76, yield: 43.8%. Ms: 1324.93

[0220] Example 10: Synthesis of Compound 82

[0221]

[0222] Synthesis of compound 10-2:

[0223] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 10-1 (21.6 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have reacted completely, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 18.6 g of compound 10-2, yield: 64.5%. Ms: 961.04.

[0224] Synthesis of compound 82:

[0225] Accurately weigh compound 10⁻² (4.8 g, 5 mmol), compound 10⁻³ (2.05 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 2.8 g of compound 82, yield: 40.4%. Ms: 1385.48

[0226] Example 11: Synthesis of Compound 90

[0227]

[0228] Synthesis of compound 11-2:

[0229] Accurately weigh compound 3-2 (21.3 g, 30 mmol), compound 11-1 (19.8 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) as eluent to obtain approximately 19.6 g of compound 11-2, yield: 68%. Ms: 961.24.

[0230] Synthesis of compound 90:

[0231] Accurately weigh compound 11-2 (4.8 g, 5 mmol), compound 11-3 (2.42 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.1 g of compound 90, yield: 44%. Ms: 1409.86

[0232] Example 12: Synthesis of Compound 94

[0233]

[0234] Synthesis of compound 12-1:

[0235] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 11-1 (19.9 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 20.3 g of compound 12-1, yield: 74.8%. Ms: 905.23.

[0236] Synthesis of compound 94:

[0237] Accurately weigh compound 12-1 (4.5 g, 5 mmol), compound 12-2 (3.54 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.1 g of compound 94. Yield: 39.3%. Ms: 1576.32

[0238] Example 13: Synthesis of Compound 97

[0239]

[0240] Synthesis of compound 13-2:

[0241] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 13-1 (14.8 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 14.3 g of compound 13-2, yield: 64.8%. Ms: 736.59.

[0242] Synthesis of compound 97:

[0243] Accurately weigh compound 13-2 (3.7 g, 5 mmol), compound 13-3 (1.61 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 2.1 g of compound 97. Yield: 41.1%. Ms: 1022.84

[0244] Example 14: Synthesis of Compound 99

[0245]

[0246] Synthesis of Compound 99:

[0247] Accurately weigh compound 13-2 (3.7 g, 5 mmol), compound 14-1 (2.0 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 2.2 g of compound 99. Yield: 40%. Ms: 1100.73

[0248] Example 15: Synthesis of Compound 123

[0249]

[0250] Synthesis of compound 15-2:

[0251] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 15-1 (27.2 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 24.3 g of compound 15-2, yield: 70.5%. Ms: 1149.47

[0252] Synthesis of compound 123:

[0253] Accurately weigh compound 15-2 (5.7 g, 5 mmol), compound 15-3 (2.63 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.7 g of compound 123. Yield: 45.2%. Ms: 1639.62

[0254] Example 16: Synthesis of Compound 126

[0255]

[0256] Synthesis of compound 16-2:

[0257] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 15-1 (30.6 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 24.1 g of compound 16-2, yield: 59%. Ms: 1261.69

[0258] Synthesis of compound 126:

[0259] Accurately weigh compound 16-2 (6.3 g, 5 mmol), compound 16-3 (2.44 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.7 g of compound 126. Yield: 43.2%. Ms: 1713.33

[0260] Example 17: Synthesis of Compound 127

[0261]

[0262] Synthesis of compound 17-2:

[0263] Accurately weigh compound 3-2 (21.3 g, 30 mmol), compound 17-1 (30.6 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water. After purging with nitrogen three times, heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 28.3 g of compound 17-2, yield: 71.6%. Ms: 1317.61

[0264] Synthesis of compound 127:

[0265] Accurately weigh compound 17-2 (6.6 g, 5 mmol), compound 17-3 (1.82 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.5 g of compound 127. Yield: 42.5%. Ms: 1645.42

[0266] Example 18: Synthesis of Compound 136

[0267]

[0268]

[0269] Synthesis of compound 18-1:

[0270] Accurately weigh compounds 1-3 (19.7 g, 30 mmol), 17-1 (30.6 g, 60 mmol), tetraphenylphosphine palladium (1.2 g, 1 mmol), and potassium carbonate (12.4 g, 90 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene and 100 mL of water, purge with nitrogen three times, and then heat to 80 °C and react overnight. After the starting materials have completely reacted, dilute with water, extract with ethyl acetate, combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 4:1 (v / v) to obtain approximately 28.4 g of compound 18-1, yield: 75%. Ms: 1261.62

[0271] Synthesis of compound 136:

[0272] Accurately weigh compound 18-1 (6.3 g, 5 mmol), compound 18-2 (2.0 g, 10 mmol), and pyridine (1.6 g, 20 mmol) into a 250 mL three-necked flask. Add approximately 120 mL of chloroform, purge with nitrogen three times, and then heat to 60 °C and react overnight. After the reactants have completely reacted, remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM as the eluent (3:1, v / v) to obtain approximately 3.5 g of compound 136. Yield: 43.1%. Ms: 1625.82

[0273] Device fabrication:

[0274] The fabrication process of the OPV device comprising the above-mentioned compounds is described in detail below through specific embodiments. The OPV device structure is as follows: Indium Tin Oxide (ITO) / PEDOT:PSS / Active Layer / PFN-Br / Ag.

[0275] The fabrication steps of device example 1 are as follows:

[0276] 1) ITO substrate cleaning:

[0277] Clean the ITO conductive glass with detergent, rinse it thoroughly, and then ultrasonically clean it for 15 minutes with deionized water, acetone, and isopropanol. After that, dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0278] 2) Preparation of the anode buffer layer

[0279] PEDOT:PSS was uniformly spin-coated onto ITO in air at a speed of 3000-4000 rpm and dried at 150°C for 15 min to obtain an anodized modification layer with a thickness of 20 nm.

[0280] 3) Preparation of photoactive layer

[0281] In a glove box (inert gas atmosphere), the photoactive layer material is uniformly spin-coated onto the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a total thickness of 100 nm; wherein the donor material in the photoactive layer material is selected from PM6:PTQ10 (mass ratio 0.8:0.2); the acceptor material is selected from compound 1; the mass ratio of the donor material to the acceptor material is 1:1.2.

[0282] 4) Preparation of cathode buffer layer

[0283] After hot annealing at 100℃ for 10 min, the cathode buffer layer material PFN-Br was uniformly spin-coated onto the active layer at a spin speed of 1800-4000 rpm to obtain a cathode buffer layer with a thickness of 5 nm.

[0284] 5) Cathode layer preparation

[0285] In high vacuum (1×10 -6 Ag was deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of 100 nm, at a deposition rate of 4 A / s.

[0286] 6) Packaging

[0287] The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0288]

[0289] Device Example 2: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 4.

[0290] Device Example 3: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 18.

[0291] Device Example 4: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 52.

[0292] Device Example 5: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 55.

[0293] Device Example 6: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 76.

[0294] Device Example 7: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 82.

[0295] Device Example 8: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 90.

[0296] Device Example 9: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 99.

[0297] Device Example 10: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 123.

[0298] Device Example 11: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 127.

[0299] Device Example 12: The preparation method is the same as that of Device Example 1, except that the acceptor material in the active layer is compound 136.

[0300] The performance of the fabricated organic solar cell device was tested. Under AM1.5G standard light irradiation using a solar simulator (SS-F5-3A), the cell current-voltage curve was measured, and the photoelectric conversion efficiency was calculated.

[0301] receptor materials Photoelectric conversion efficiency (%) Device Example 1 Compound 1 12.84 Device Example 2 Compound 4 13.61 Device Example 3 Compound 18 13.15 Device Example 4 Compound 52 14.23 Device Example 5 Compound 55 12.37 Device Example 6 Compound 76 13.87 Device Example 7 Compound 82 14.90 Device Example 8 Compound 90 13.38 Device Example 9 Compound 99 12.49 Device Example 10 Compound 123 14.78 Device Example 11 Compound 127 13.56 Device Example 12 Compound 136 14.34

[0302] As can be seen from the device characterization of the above-described device embodiments, the compound protected in this application selects a seven-membered nitrogen heterocyclic core, introduces a suitable electron-donating core, and connects it with a terminal electron-withdrawing group A, giving it good charge mobility and a suitable energy level. The seven-membered nitrogen heterocyclic organic compound described in this application can be used as a small molecule acceptor material in organic solar cell devices, thereby improving the photoelectric conversion efficiency of the device.

[0303] The above embodiments further illustrate the content of this application, but should not be construed as limiting the application. Modifications and substitutions made to the methods, steps, or conditions of this application without departing from the spirit and substance of this application are all within the scope of this application. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

Claims

1. An organic compound containing a seven-membered nitrogen heterocycle, characterized in that: It has a structure as shown in general formula (I): in, Ar1 and Ar2 are independently selected from structural formulas (A-1), (A-2), (A-3), or (A-4): in, W is selected from CR 11 R 12 ; Each time R0 appears, it is independently selected from: a straight-chain alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 Each occurrence is independently selected from: -H, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 cyclic atoms, or a group formed by a combination of the above groups; * indicates a connection point; EG1 and EG2 are independently selected from the following groups: Among them, R 14 Each occurrence is independently selected from -H, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, cyano, nitro, -Cl, -Br, -F, -I, or groups formed by combinations of the above groups.

2. The organic compound containing a seven-membered nitrogen heterocycle according to claim 1, characterized in that: The seven-membered nitrogen heterocyclic organic compound is selected from general formula (II-1), general formula (II-2), general formula (II-3) or general formula (II-4):

3. A seven-membered nitrogen heterocyclic organic compound according to claim 1 or 2, characterized in that: R0 is selected from: straight-chain alkyl groups having 1 to 15 carbon atoms, or branched or cyclic alkyl groups having 3 to 15 carbon atoms.

4. An organic compound containing a seven-membered nitrogen heterocycle according to claim 1 or 2, characterized in that: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 The group is independently selected from: -H, a straight-chain alkyl group having 1 to 15 carbon atoms, a branched or cyclic alkyl group having 3 to 15 carbon atoms, an aromatic group having 6 to 10 cyclic atoms, or a group formed by a combination of the above groups.

5. The organic compound containing a seven-membered nitrogen heterocycle according to claim 1, characterized in that: The seven-membered nitrogen heterocyclic organic compound is selected from the following structural formulas:

6. A mixture, characterized in that: The mixture comprises the seven-membered nitrogen heterocyclic organic compound as described in any one of claims 1-5 and at least one organic functional material, wherein the organic functional material is selected from active layer donor materials.

7. A mixture, characterized in that: The mixture comprises the seven-membered nitrogen heterocyclic organic compound as described in any one of claims 1-5 and at least one organic functional material, wherein the organic functional material is selected from active layer acceptor materials.

8. An electron acceptor material, characterized in that: The electron acceptor material is selected from the seven-membered nitrogen heterocyclic organic compounds according to any one of claims 1-5 or the mixtures according to claim 7.

9. An organic electronic device comprising at least one functional layer, characterized in that: The functional layer material is selected from the seven-membered nitrogen heterocyclic organic compound according to any one of claims 1-5, or the mixture according to claim 6, or the mixture according to claim 7.

Images