A fused heterocyclic organic compound, its end group and application thereof

Abstract

The present application relates to the field of organic photovoltaic materials, and in particular to a fused heterocyclic organic compound, a terminal group thereof and application thereof. The fused heterocyclic organic compound provided by the present application enhances the intramolecular charge transfer effect by connecting a terminal group structure with strong electron-withdrawing capacity, expands the absorption of the electron acceptor in the near-infrared region, and applies the fused heterocyclic organic compound as an organic photovoltaic acceptor material to a photoactive layer, so as to widen the range of the absorption spectrum, improve the light capturing capacity of the photoactive layer, optimize the vertical phase separation of the photoactive layer, effectively promote the generation, transportation and collection of charge carriers, and thus improve the photoelectric performance of the device.

Description

Technical Field

[0001] This invention relates to the field of organic photovoltaic materials, specifically to a fused heterocyclic organic compound, its end groups, and its applications. Background Technology

[0002] In recent years, with the continuous and in-depth research on organic photovoltaic materials and device engineering, organic photovoltaic technology has also achieved rapid development. Currently, the mainstream organic photovoltaic acceptor materials are mainly selected from ADA-type non-fullerene acceptor materials, where A is the electron-withdrawing terminal group and D is the central core. Unlike fullerene acceptor materials, the molecular structure of non-fullerene acceptor materials is easier to modify, and their absorption, energy levels, and stacking properties are easier to adjust.

[0003] For electron-withdrawing terminal groups A in non-fullerene acceptor materials, there are currently three main categories: the first category is based on halogen substitution or non-substitution. ,like , Specific compound structures include, but are not limited to, ITIC, IT-4F, IT-4Cl, Y6, L8-BO, BTP-eC9, etc. The second category is based on halogen substitution or non-substitution. ,like , Specific compound structures include, but are not limited to, Z7, Z8, BT-L4F, BT-BO-L4F, etc. The third category is based on halogen substitution or non-substitution. or ,like , , , Specific high-efficiency compounds include ITCC, ITCC-Cl, FCC-Cl, and FTCC-Br. The third type of end groups is mainly used in the structure of organic compounds for indoor photovoltaics. Currently, the end groups of non-fullerene acceptor materials under sunlight are mainly selected from the first and second types, resulting in narrow selectivity and severely hindering the further development of current acceptor materials.

[0004] Therefore, there is an urgent need to develop a compound containing novel end groups to enrich and optimize the structure of non-fullerene acceptor materials, which is crucial for the development of organic photovoltaic technology. Summary of the Invention

[0005] The purpose of this invention is to address the limitations of current acceptor materials due to the limited selectivity of terminal A groups and the lack of related research. The invention aims to develop an organic compound with a novel terminal structure to serve as an organic photovoltaic acceptor material. By effectively regulating the energy level, absorption, and stacking of the compound through the terminal structure, the compound exhibits excellent photoelectric properties.

[0006] A first aspect of this invention develops a fused heterocyclic organic compound having a structure as shown in general formula (I): (I) in: Selected from any of the following groups:

[0007] Each time R1 and R2 appear, they are independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl groups having 1-10 carbon atoms, alkoxy groups having 1-10 carbon atoms, or alkylthio groups having 1-10 carbon atoms. * indicates a connection point; Ar1 is selected from substituted or unsubstituted heteroaromatic groups having 10-50 ring atoms; The term "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents R, wherein each substituent R is independently selected from: -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl having 1-30 carbon atoms, alkoxy having 1-30 carbon atoms, alkylthio having 1-30 carbon atoms, ester having 1-30 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a combination of at least two of these.

[0008] Furthermore, the fused heterocyclic organic compound has a structure as shown in general formula (II-1), (II-2), or (II-3):

[0009] .

[0010] In an optional embodiment, each occurrence of R1 and R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-6 carbon atoms, branched alkyl with 3-6 carbon atoms, straight-chain alkoxy with 1-6 carbon atoms, branched alkoxy with 3-6 carbon atoms, straight-chain alkylthio with 1-6 carbon atoms, or branched alkylthio with 3-6 carbon atoms.

[0011] Furthermore, each occurrence of R1 and R2 is independently selected from -H, -D, -F, -Cl, -Br, or -I.

[0012] In an optional embodiment, the Ar1 is selected from substituted or unsubstituted heteroaromatic groups having 10-40 ring atoms; the heteroatoms in the heteroaromatic group are selected from N, O, S or Se.

[0013] Furthermore, Ar1 is selected from (B-1) or (B-2):

[0014] in: Ar2 is selected from R a Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; Each time Ar3 and Ar4 appear, they are selected independently. or ; Each time Z appears, it is independently selected from O, S, or Se; Each time R3 and R4 appear, they are independently selected from the list of R. b Substituted or unsubstituted straight-chain alkyl groups having 1-30 carbon atoms, subject to R b Substituted or unsubstituted branched alkyl groups having 3-30 carbon atoms, R c Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or R c Aromatic groups having 6-10 carbon atoms, substituted or unsubstituted; Each time R5 appears, it is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl groups having 1-10 carbon atoms, or alkoxy groups having 1-10 carbon atoms; Each time R6 appears, it is independently selected from -H, -D, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, or branched alkylthio with 3-20 carbon atoms; R a R c Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched alkylthio with 3-20 carbon atoms, ester group with 1 to 20 carbon atoms, aromatic group with 6-20 carbon atoms, and heteroaromatic group with 5-20 cyclic atoms. Rb Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, aromatic groups having 6-20 carbon atoms, and heteroaromatic groups having 5-20 ring atoms; # indicates a fusion site, which is selected from carbon atoms.

[0015] In an alternative embodiment, (B-1) is selected from the following structures: .

[0016] In an alternative embodiment, (B-2) is selected from any of the following structures: .

[0017] In an alternative embodiment, Z is selected from S or Se.

[0018] In an alternative embodiment, the Ar2 is selected from R a Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms.

[0019] In an alternative embodiment, the Ar2 is selected from any of the following groups:

[0020] in: Each time X appears, it is independently selected from CR7 or N; Y is selected from O, S, or Se; Each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl groups having 1-20 carbon atoms, branched-chain alkyl groups having 3-20 carbon atoms, cycloalkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched-chain alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched-chain alkylthio groups having 3-20 carbon atoms, ester groups having 1-20 carbon atoms, and R. d Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, and R d One or a combination of at least two of the following heteroaromatic groups, substituted or unsubstituted, having 5-20 ring atoms; the R d Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-20 carbon atoms, or branched alkyl with 3-20 carbon atoms.

[0021] Furthermore, each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl groups having 1-10 carbon atoms, branched-chain alkyl groups having 3-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, straight-chain alkoxy groups having 1-10 carbon atoms, branched-chain alkoxy groups having 3-10 carbon atoms, straight-chain alkylthio groups having 1-10 carbon atoms, branched-chain alkylthio groups having 3-10 carbon atoms, ester groups having 1 to 10 carbon atoms, and R... d Substituted or unsubstituted phenyl, R d One or a combination of at least two of the substituted or unsubstituted thiophene groups; the R d Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-10 carbon atoms, or branched alkyl with 3-10 carbon atoms.

[0022] Furthermore, the Ar2 is selected from any of the following groups: .

[0023] In an alternative embodiment, each occurrence of R3 is independently selected from the R... b Substituted or unsubstituted straight-chain alkyl groups having 6-20 carbon atoms, by R b Substituted or unsubstituted branched alkyl groups having 6-20 carbon atoms; further, the R b Each time it appears, it is independently selected from R. e Substituted or unsubstituted phenyl, R e Substituted or unsubstituted thiophene group; the R e Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, straight-chain alkoxy with 1-10 carbon atoms, or branched alkoxy with 3-10 carbon atoms.

[0024] Furthermore, each occurrence of R3 is independently selected from any of the following groups, but is not limited to: .

[0025] In an alternative embodiment, each occurrence of R4 is independently selected from the R... b Substituted or unsubstituted straight-chain alkyl groups having 1-20 carbon atoms, subject to R b Substituted or unsubstituted branched alkyl groups having 3-20 carbon atoms, R cSubstituted or unsubstituted phenyl; further, the R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-20 carbon atoms, and branched alkyl with 3-20 carbon atoms.

[0026] Furthermore, each occurrence of R4 is independently selected from the subset of R. c Substituted or unsubstituted phenyl; further, the R c Each occurrence is independently selected from straight-chain alkyl groups having 1-20 carbon atoms or branched alkyl groups having 3-20 carbon atoms.

[0027] In an alternative embodiment, each occurrence of R5 is independently selected from -H, -D, -F, -Cl, -CN, -CF3, a straight-chain alkyl group having 1-10 carbon atoms, or a branched alkyl group having 3-10 carbon atoms.

[0028] In an optional embodiment, each occurrence of R6 is independently selected from -H, -D, a straight-chain alkyl group having 1-16 carbon atoms, a branched alkyl group having 3-16 carbon atoms, a cycloalkyl group having 3-16 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a branched alkoxy group having 3-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, or a branched alkylthio group having 3-16 carbon atoms.

[0029] Furthermore, each occurrence of R6 is independently selected from -H, -D, or any of the following groups, but not limited to: .

[0030] In one specific embodiment, the fused heterocyclic organic compound according to the present invention is selected from any of the following structures, but is not limited thereto: .

[0031] A second aspect of the present invention relates to an end base selected from structures shown in general formula (III): (III) Wherein: R8 is selected independently each time it appears from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, or alkylthio with 1-10 carbon atoms; In one specific embodiment, the end base is selected from any of the following structures: .

[0032] A third aspect of the present invention provides a synthetic route for the end group of general formula (III), as shown below: .

[0033] A fourth aspect of the invention relates to a mixture comprising a fused heterocyclic organic compound as described in the first aspect.

[0034] Furthermore, the mixture further comprises at least one photoactive layer donor material.

[0035] In one embodiment, the photoactive layer donor material is selected from polymer donor materials. The polymer donor material may 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 benzodithiophene (BDT), benzothiadiazoles (BT, BBT), quinoxalines (QU, PQ), pyrazines (TP, PQ), and copolymers with electron-rich groups (such as thiophene derivatives), such as PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PB2, PCE10, etc., but is not limited to these.

[0036] In one embodiment, the mixture further comprises another photoactive layer receptor material.

[0037] Preferably, the other photoactive layer acceptor material is selected from one or more of the following: ITIC-based acceptor materials, including but not limited to: ITIC, ITIC-4F, ITIC-4Cl, ITIC-2F, ITIC-M, ITCC, ITCC-Cl, etc.; Y-type acceptor materials, including but not limited to: Y6, L8-BO, BTP-eC9, N3, N4, Y6-O, HDO-4Cl, BTP-H2, PY-IT, etc.; FCC-type acceptor materials, including but not limited to: FCC-Cl, FTCC-Br, etc.; and fullerene-based acceptor materials, including but not limited to: PC61BM ([6,6]-phenyl C61 butyrate methyl ester), PC71BM ([6,6]-phenyl C71 butyrate methyl ester), indene-containing fullerene, etc.

[0038] The fifth aspect of the present invention relates to a composition comprising a fused heterocyclic organic compound as described in the first aspect, or a mixture as described in the fourth aspect, and at least one organic solvent.

[0039] The organic solvent is selected from, but not limited to: tetrahydronaphthalene, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decahydronaphthalene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,4-dimethylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, acetophenone, diphenyl ether, 2-methylthiophene, 3-methylthiophene, monochloromethane, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,2-trichlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2 One or a mixture of two or more of the following: 4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-dioxane, N-methylpyrrolidone, acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, carbon disulfide, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, indane, methyl benzoate, ethyl benzoate, acetonitrile, and hexamethylphosphoramide.

[0040] The organic solvent may further include additives for adjusting viscosity, film-forming properties, and improving adhesion. The additives may be selected from, but are not limited to, 1,8-diiodooctane (DIO), diphenyl ether (DPE), anthracene, 1,4-diiodobenzene (DIB), 1,3-dibromo-5-chlorobenzene (DBCl), 3,5-dichlorobromobenzene (DCBB), 1-chloronaphthalene (1-CN), 1,3,5-tribromobenzene (TBB), etc., but are not limited to these.

[0041] The sixth aspect of the present invention relates to an organic photovoltaic device comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, the photoactive layer comprising a fused heterocyclic organic compound as described in the first aspect, or a mixture as described in the fourth aspect, or a composition as described in the fifth aspect.

[0042] The preparation method of the photoactive layer material solution is as follows: the photoactive layer donor material and / or acceptor material are dissolved in an organic solvent at a certain mass ratio, and stirred evenly to obtain a photoactive layer solution.

[0043] The above solution is used to prepare the photoactive layer by printing or coating methods. These printing or coating methods can include, but are 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, and slot-loaded extrusion coating. Slot-loaded coating, spin coating, and inkjet printing are preferred.

[0044] At least one of the anode and cathode is transparent or translucent to facilitate light incidence. The material used to prepare the electrode 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), palladium (Pd), or alloys of the above metals; conductive nanomaterials such as metal nanowires, nanoparticle pastes, graphene, carbon nanotubes; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; and conductive polymers such as PEDOT:PSS, polypyrrole, and polyaniline; or composite structures having multiple layers of electrode materials, such as metal / ITO (or ITO / metal), and ITO / metal / ITO, AZO / metal / AZO, etc., but not limited to these.

[0045] In one embodiment, the organic photovoltaic device comprises an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked sequentially, wherein the photoactive layer comprises a fused heterocyclic organic compound as described in the first aspect, or a mixture as described in the fourth aspect, or is prepared from a composition as described in the fifth aspect.

[0046] Preferably, the cathode buffer layer material can be selected from low work function metal complexes, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, PEI-Zn, LiF, titanium oxide (TiO2). xIt can be zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be polymer materials, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited to these.

[0047] The anode buffer layer material is selected from PEDOT:PSS and molybdenum oxide (MoO). x ), vanadium oxide (V₂O₅), nickel oxide (NiOx), tungsten oxide (WO₂) x Preferably, x is selected from 2 or 3), small molecule self-assembled materials such as 2PACz, MeO-2PACz, etc., but not limited to these.

[0048] It should be noted that, in order to improve the performance of organic photovoltaic devices, the organic photovoltaic devices may further include other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0049] Furthermore, organic photovoltaic devices also include a substrate.

[0050] In one embodiment, the substrate is disposed on the anode side and away from the photoactive layer; in another embodiment, the substrate is disposed on the cathode side and away from the photoactive layer.

[0051] 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 films in the form of single or multiple layers, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), parylene, etc., but is not limited to these, and substrates commonly used in organic solar cells may also be used.

[0052] The organic photovoltaic devices described in this invention are mainly used in indoor photovoltaics, wearable devices, smart IoT, smart homes, smart agriculture, building photovoltaics, new energy vehicles and other fields.

[0053] The beneficial effects of this invention are: This invention provides a fused heterocyclic organic compound by connecting end groups with strong electron-withdrawing capabilities. This enhances the intramolecular charge transfer effect, expands the absorption of electron acceptors in the near-infrared region, and when used as an organic photovoltaic acceptor material in the photoactive layer, it can broaden the absorption spectrum range, improve the light-harvesting ability of the photoactive layer, optimize the vertical phase separation of the photoactive layer, and effectively promote the generation, transport and collection of charge carriers, thereby improving the optoelectronic performance of the device. Attached Figure Description

[0054] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0055] Figure 1 This is the 1H NMR spectrum of the terminal group (E-1) of this application.

[0056] Figure 2 This is a schematic diagram of the structure of the organic photovoltaic device described in the device embodiments of this application. Detailed Implementation

[0057] 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. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention without inventive effort are within the scope of protection of this invention.

[0058] 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").

[0059] In this invention, organic photovoltaic devices, organic solar cells, OPV, and OSC have the same meaning and can be used interchangeably.

[0060] In this invention, the terms "photoactive layer" and "active layer" have the same meaning and can be used interchangeably.

[0061] In this invention, when the same group contains multiple substituents with the same symbol, the substituents can be the same or different from each other. For example, the six Rs on the benzene ring can be the same or different from each other.

[0062] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0063] 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. In aromatic groups, the ring atom number is the same as the carbon atom number; in heteroaromatic groups, the ring atom number is the carbon atom number plus the heteroatom number; for example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, the ring atom number of a quinoline ring is 10, the ring atom number of a thiophene group is 5, and the ring atom number of a thiophene is 8.

[0064] In this invention, "aromatic group" refers to any optional functional group or substituent derived from an aromatic carbon ring. The aromatic group can be a monocyclic aryl (e.g., phenyl) or a polycyclic aryl; in other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated by carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise stated, two or more aromatic groups conjugated by carbon-carbon bonds can also be considered as the aromatic group of this application. Preferably, the aromatic group is selected from aromatic groups having 6-30 carbon atoms; further, it is selected from aromatic groups having 6-20 carbon atoms; further, it is selected from aromatic groups having 6-10 carbon atoms; the aromatic group includes, but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives.

[0065] In this invention, a "heteroaromatic group" refers to a heteroaromatic ring or its derivative containing one, two, three, four, five, six or more heteroatoms, wherein the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl or a polycyclic heteroaryl. The term "heteroaromatic group" as used herein also includes groups formed by the fusion of one or more heteroaromatic groups with one or more aromatic rings, aliphatic rings or heterocycles. Preferably, the heteroaromatic group is selected from those having 5-30 ring atoms; further, it is selected from those having 5-20 ring atoms; and further, it is selected from those having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to: thiophene, furanyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridinyl, bipyridinyl, pyrimidinyl, triazinyl, acridineyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrol, thienopyrrol, thienopyrrol, furanol, furanol, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridine, primidyl, quinazolinone, dibenzothiophene, dibenzofuranyl, carbazole and their derivatives.

[0066] In this invention, alkyl refers to straight-chain alkyl, branched-chain alkyl, cycloalkyl, and combinations thereof. The number of carbon atoms in a straight-chain alkyl group can be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms in a branched-chain alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of straight-chain alkyl groups include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), and n-pentyl (-C5H9). 11 ), n-hexyl (-C6H) 13 ), heptyl (-C7H) 15 ), octyl (-C8H) 17 ), non-nonyl (-C9H) 19 -C 10 H 21 -C 11 H 23 -C 12 H 25 -C 13 H 27 -C 14 H 29 -C 15 H 31 -C 16 H 33Non-limiting examples of branched alkyl groups include: isopropyl, branched alkyl groups containing 4 carbon atoms, branched alkyl groups containing 5 carbon atoms, branched alkyl groups containing 6 carbon atoms, branched alkyl groups containing 7 carbon atoms, branched alkyl groups containing 8 carbon atoms, branched alkyl groups containing 9 carbon atoms, branched alkyl groups containing 10 carbon atoms, branched alkyl groups containing 11 carbon atoms, branched alkyl groups containing 12 carbon atoms, branched alkyl groups containing 13 carbon atoms, branched alkyl groups containing 14 carbon atoms, branched alkyl groups containing 15 carbon atoms, and branched alkyl groups containing 16 carbon atoms.

[0067] The term "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to other groups via an oxygen atom. The straight-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0068] The term "alkoxythio" refers to a group with the structure "-S-alkyl", that is, an alkyl group as defined above that is attached to other groups via a sulfur atom. The straight-chain alkoxythio group indicates that the alkyl group in the "-S-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxythio group indicates that the alkyl group in the "-S-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0069] 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.

[0070] 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.

[0071] 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 connected to any substituted site on the benzene ring.

[0072] In describing the structural elements of the present invention, the terms "comprising" or "including" or similar terms used in the present invention mean that the device or material preceding the word covers the device or material listed after the word and its equivalents, but does not exclude other devices or materials.

[0073] In the description of this invention, it should be understood that the terms "upper," "lower," "between layers," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly used when organic solar cell devices are in use, or the orientation or positional relationship commonly understood by those skilled in the art. They are only used to facilitate the description of this invention and to simplify the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0074] 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 groups listed.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] Compound Synthesis Examples The following embodiments are provided to facilitate a better understanding of the disclosure of this invention, but are not intended to limit it in any way. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the materials and reagents used are prior art and commercially available unless otherwise specified.

[0079] End-group (E-1) synthesis:

[0080] Synthesis of compounds 1-2: Accurately weigh compound 1-1 (28.8 g, 200.0 mmol), ethyl hydroxyacetate (104 g, 1.00 mol), and lithium bromide (17.4 g, 200 mmol) into a 500 mL three-necked flask. Purge with nitrogen three times and heat the reaction mixture to 110 °C with stirring for 8 h. After the reaction is complete, cool to room temperature, pour the reaction mixture into water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, filter, concentrate under vacuum, and purify by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield is approximately 29.47 g of compound 1-2, yield: 79.9%, MS: 184.41.

[0081] Synthesis of compounds 1-3: Compounds 1-2 (22.1 g, 120 mmol) were accurately weighed and dissolved in DCM (dichloromethane, 500 mL). The solution was stirred at room temperature, and pyridinium chlorochromate (PCC) (32.4 g, 150 mmol) was added in five portions. After 12 h, the reaction mixture was poured into water, quenched with sodium sulfite, filtered under reduced pressure, and extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under vacuum, and purified by column chromatography using a mixture of petroleum ether and dichloromethane as eluent. The final yield was approximately 18.83 g of compounds 1-3, yield: 85.7%, MS: 182.94.

[0082] Synthesis of compounds 1-4: Compounds 1-3 (14.6 g, 80 mmol) were accurately weighed and dissolved in a mixed solution of THF (tetrahydrofuran, 300 mL) and triethylamine (30 mL). The solution was purged with nitrogen three times, stirred at room temperature, and then acetyl chloride (10.2 g, 160 mmol) was slowly added dropwise. Stirring continued for 3 h. After the reaction was complete, the reaction solution was poured into water and extracted three times with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate, filtered, concentrated under vacuum, and purified by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. The final yield was approximately 14.95 g of compounds 1-4, yield: 83.3%, MS: 224.38.

[0083] Synthesis of compounds 1-5: Compounds 1-4 (13.5 g, 60.0 mmol) were accurately weighed and dissolved in THF (200 mL). The solution was purged with nitrogen three times and cooled to -20 °C, then held at this temperature for 30 minutes. 1,8-diazobispiro[5.4.0]undec-7-ene (DBU, 20 mL) was then added dropwise. After the addition was complete, the mixture was transferred to room temperature and stirred for 1 h. The reaction solution was poured into water and extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under vacuum, and purified by column chromatography using a mixture of petroleum ether and dichloromethane as eluent. The final yield was approximately 4.70 g of compounds 1-5, yield: 34.9%, MS: 224.13.

[0084] Synthesis of compounds 1-6: Compounds 1-5 (4.48 g, 20.0 mmol) were accurately weighed and dissolved in DCM (150 mL). The solution was stirred at room temperature, and PCC (5.40 g, 25.0 mmol) was added in five portions. After 12 h, the reaction mixture was poured into water, quenched with sodium sulfite, filtered under reduced pressure, and extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under vacuum, and purified by column chromatography using a mixture of petroleum ether and dichloromethane as eluent. The final yield was approximately 3.32 g of compounds 1-6, yield: 74.7%, MS: 222.34.

[0085] Synthesis of compound (E-1): Compounds 1-6 (2.22 g, 10.0 mmol) and malononitrile (1.00 g, 15.0 mmol) were accurately weighed and dissolved in DMSO (80 mL). The mixture was purged with nitrogen three times. Potassium acetate (2.00 g, 20.0 mmol) was added in portions, and the mixture was stirred at room temperature for 1 h. After the reaction was complete, the reaction solution was poured into water and extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under vacuum, and purified by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. The final yield was approximately 1.72 g of compound (E-1), with a yield of 63.7%. The NMR spectrum of compound (E-1) is shown below. Figure 1 As shown.

[0086] End-group (E-2) synthesis:

[0087] Synthesis of compound 2-2: The synthesis of compound 2-2 was similar to that of compound 1-2, except that compound 1-1 was replaced with an equimolar amount of compound 2-1, yielding approximately 35.41 g of compound 2-2, yield: 81.7%, MS: 216.59.

[0088] Synthesis of compounds 2-3: The synthesis of compounds 2-3 was similar to that of compounds 1-3, except that compounds 1-2 were replaced with an equimolar amount of compound 2-2, yielding approximately 19.85 g of compound 2-3, yield: 77.0%, MS: 214.74.

[0089] Synthesis of compounds 2-4: The synthesis of compounds 2-4 was similar to that of compounds 1-4, except that compounds 1-3 were replaced with an equimolar amount of compounds 2-3, yielding approximately 16.53 g of compounds 2-4. Yield: 80.6%, MS: 256.28.

[0090] Synthesis of compounds 2-5: The synthesis of compounds 2-5 was similar to that of compounds 1-5, except that compounds 1-4 were replaced with an equimolar amount of compounds 2-4, yielding approximately 6.23 g of compounds 2-5, yield: 40.5%, MS: 256.21.

[0091] Synthesis of compounds 2-6: The synthesis of compounds 2-6 was similar to that of compounds 1-6, except that compounds 1-5 were replaced with an equimolar amount of compounds 2-5, yielding approximately 3.72 g of compounds 2-6, yield: 72.7%, MS: 255.73.

[0092] Synthesis of compound (E-2): The synthesis of compound (E-2) was based on the synthesis of compound (E-1), except that compounds 1-6 were replaced with equimolar amounts of compounds 2-6, yielding approximately 1.81 g of compound (E-2), yield: 59.8%, MS: 302.49.

[0093] Compound Synthesis Example 1: Synthesis of Compound (4)

[0094] Accurately weigh compound A-4 (106 mg, 0.1 mmol) and compound E-1 (95 mg, 0.35 mmol) into a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. Finally, approximately 119 mg of compound (4) was obtained, yield: 76.3%, MALDI-TOF-MS: 1559.20.

[0095] Compound Synthesis Example 2: Synthesis of Compound (6)

[0096] Accurately weigh compound A-6 (126 mg, 0.1 mmol) and compound E-1 (95 mg, 0.35 mmol), add them to a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, approximately 138 mg of compound (6) was obtained, yield: 78.1%, MALDI-TOF-MS: 1766.88.

[0097] Compound Synthesis Example 3: Synthesis of Compound (9)

[0098] Accurately weigh compound A-9 (108 mg, 0.1 mmol) and compound E-2 (106 mg, 0.35 mmol), add them to a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, about 135 mg of compound (9) was obtained, yield: 81.6%, MALDI-TOF-MS: 1653.41.

[0099] Compound Synthesis Example 4: Synthesis of Compound (13)

[0100] Accurately weigh compound A-13 (145 mg, 0.1 mmol) and compound E-2 (106 mg, 0.35 mmol), add them to a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. Finally, about 150 mg of compound (13) was obtained, yield: 74.4%, MALDI-TOF-MS: 2016.57.

[0101] Compound Synthesis Example 5: Synthesis of Compound (19)

[0102] Accurately weigh compound A-19 (133 mg, 0.1 mmol) and compound E-1 (95 mg, 0.35 mmol), add them to a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, approximately 148 mg of compound (19) was obtained, yield: 80.6%, MALDI-TOF-MS: 1836.74.

[0103] Compound Synthesis Example 6: Synthesis of Compound (22)

[0104] Accurately weigh compound A-22 (130 mg, 0.1 mmol) and compound E-1 (95 mg, 0.35 mmol), add them to a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, approximately 135 mg of compound (22) was obtained, with a yield of 74.8% and MALDI-TOF-MS: 1803.97.

[0105] Compound Synthesis Example 7: Synthesis of Compound (26)

[0106] Accurately weigh compound A-26 (102 mg, 0.1 mmol) and compound E-1 (95 mg, 0.35 mmol), add them to a 50 mL three-necked flask, then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, approximately 121 mg of compound (26) was obtained, with a yield of 79.5% and MALDI-TOF-MS: 1523.48.

[0107] Compound Synthesis Example 8: Synthesis of Compound (33)

[0108] Synthesis of compound (B-33): Accurately weigh compound A-4 (528 mg, 0.5 mmol) and compound E-1 (149 mg, 0.55 mmol) into a 50 mL three-necked flask, followed by tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction mixture into methanol, precipitate a solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield was approximately 231 mg of compound (B-33), yield: 35.3%, MALDI-TOF-MS: 1307.61.

[0109] Synthesis of compound (33): Accurately weigh compound B-33 (65 mg, 0.05 mmol) and 5,6-difluoro-3-(dicyanomethylene)indene-1-one (17 mg, 0.075 mmol) into a 50 mL three-necked flask, followed by the addition of tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. Finally, approximately 65 mg of compound (33) was obtained, yield: 85.7%, MALDI-TOF-MS: 1519.38.

[0110] Compound Synthesis Example 9: Synthesis of Compound (36)

[0111] Synthesis of compound (B-36): Accurately weigh compound A-36 (583 mg, 0.5 mmol) and compound E-1 (149 mg, 0.55 mmol) into a 50 mL three-necked flask, followed by the addition of tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction mixture into methanol, and precipitate a solid. Filter the solid, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield was approximately 217 mg of compound (B-36), yield: 30.6%, MALDI-TOF-MS: 1420.22.

[0112] Synthesis of compound (36): Accurately weigh compound B-36 (71 mg, 0.05 mmol), 2-(6,7-difluoro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malononitrile (21 mg, 0.075 mmol), and add them to a 50 mL three-necked flask. Then add tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, about 63 mg of compound (36) was obtained, with a yield of 74.9% and MALDI-TOF-MS: 1681.95.

[0113] Compound Synthesis Example 10: Synthesis of Compound (39)

[0114] Synthesis of compound (B-39): Accurately weigh compound A-39 (220 mg, 0.2 mmol) and compound E-2 (67 mg, 0.22 mmol) into a 50 mL three-necked flask, followed by tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction mixture into methanol, precipitate a solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield was approximately 103 mg of compound (B-39), yield: 37.1%, MALDI-TOF-MS: 1387.14.

[0115] Synthesis of compound (39): Accurately weigh compound B-39 (69 mg, 0.05 mmol) and 5,6-dichloro-3-(dicyanomethylene)indene-1-one (20 mg, 0.075 mmol) into a 50 mL three-necked flask, followed by the addition of tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, approximately 63 mg of compound (39) was obtained, yield: 77.2%, MALDI-TOF-MS: 1632.80.

[0116] Compound Synthesis Example 11: Synthesis of Compound (46)

[0117] Synthesis of compound (B-46): Accurately weigh compound A-46 (238 mg, 0.2 mmol) and compound E-1 (59 mg, 0.22 mmol) into a 50 mL three-necked flask, followed by tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction mixture into methanol, precipitate a solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield was approximately 115 mg of compound (B-46), yield: 39.8%, MALDI-TOF-MS: 1443.94.

[0118] Synthesis of compound (46): Accurately weigh compound B-46 (72 mg, 0.05 mmol) and 5,6-difluoro-3-(dicyanomethylene)inden-1-one (17 mg, 0.075 mmol) into a 50 mL three-necked flask, followed by the addition of tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction mixture into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield was approximately 65 mg of compound (46), yield: 78.5%, MALDI-TOF-MS: 1656.37.

[0119] Compound Synthesis Example 12: Synthesis of Compound (49)

[0120] Synthesis of compound (B-49): Accurately weigh compound A-49 (250 mg, 0.2 mmol) and compound E-1 (59 mg, 0.22 mmol) into a 50 mL three-necked flask, followed by tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction mixture into methanol, precipitate a solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as eluent. The final yield was approximately 106 mg of compound (B-49), yield: 35.3%, MALDI-TOF-MS: 1499.78.

[0121] Synthesis of compound (49): Accurately weigh compound B-49 (75 mg, 0.05 mmol) and 5,6-difluoro-3-(dicyanomethylene)indene-1-one (17 mg, 0.075 mmol) into a 50 mL three-necked flask, followed by the addition of tetrahydrofuran (10 mL) and pyridine (1 mL). Purge with nitrogen three times and stir at 50 °C for 6 h. Cool to room temperature, pour the reaction solution into methanol, precipitate the solid, filter, and purify the remaining solid by column chromatography using a mixed solvent of petroleum ether and dichloromethane as the eluent. Finally, approximately 71 mg of compound (49) was obtained, with a yield of 82.9% and MALDI-TOF-MS: 1712.29.

[0122] OPV device examples Device Example 1 Device structure such as Figure 2 As shown, the organic photovoltaic device includes a substrate, an anode layer, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode layer stacked sequentially; wherein, the materials of the anode layer, the anode buffer layer, the photoactive layer, the cathode buffer layer, and the cathode layer are, in sequence: indium tin oxide (ITO) / PEDOT:PSS / Active layer / PDINN / Ag. Its preparation method includes the following steps: 1) ITO substrate cleaning Clean the ITO conductive glass with detergent, rinse thoroughly, 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.

[0123] 2) Preparation of the anode buffer layer PEDOT:PSS (Clevios™ PVP Al 4083) was uniformly spin-coated onto ITO in air at a speed of 4000 rpm for 30 s, and then dried at 150°C for 15 min to obtain an anodic buffer layer.

[0124] 3) Preparation of photoactive layer In a glove box (inert gas atmosphere), the photoactive layer material solution is uniformly spin-coated onto the anode buffer layer at a speed of 1800-3000 rpm to obtain a photoactive layer with a total thickness of approximately 100 nm. The photoactive layer material solution is prepared by dissolving the donor material and the acceptor material in chloroform to obtain the photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer PM6, the host acceptor material is selected from BTP-eC9, the guest acceptor material is selected from compound (4), and the liquid additive is selected from 1,8-diiodooctane. PM6:BTP-eC9:compound (4) is added to the chloroform solution at a mass ratio of 1:1.1:0.1, with a total concentration of 16.5 mg / mL, and the volume ratio of 1,8-diiodooctane in the chloroform is 0.5%.

[0125] 4) Preparation of cathode buffer layer The device with the photoactive layer was heat-annealed on a hot stage at 95°C for 10 min. Then, the cathode buffer layer material PDINN (PDINN was dissolved in methanol to prepare a solution with a concentration of 1.0 mg / mL) was uniformly spin-coated onto the photoactive layer at a spin speed of 3000 rpm for 30 s to obtain the cathode buffer layer.

[0126] 5) Cathode layer preparation In high vacuum (1×10 -6 Ag is deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of approximately 100 nm. 6) Packaging The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0127] Device Examples 2-10 The preparation methods of device examples 2-10 are the same as those of device example 1, the difference being the selection of the photoactive layer guest acceptor material. Specifically, the guest acceptor material compound (4) in device example 1 is replaced with compound (6), compound (9), compound (13), compound (19), compound (33), compound (36), compound (39), compound (46), and compound (49), respectively. See Table 1 for details.

[0128] Device Comparison Example 1 The fabrication method of Device Comparative Example 1 is the same as that of Device Example 1, except that the preparation method of the photoactive layer material solution is different, specifically: The method for preparing the photoactive layer material solution is as follows: The donor material and the acceptor material are dissolved in chloroform to obtain the photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer PM6, the acceptor material is selected from BTP-eC9, and the liquid additive is selected from 1,8-diiodooctane. PM6:BTP-eC9 is added to the chloroform solution at a mass ratio of 1:1.2, with a total concentration of 16.5 mg / mL, and the volume ratio of 1,8-diiodooctane in the chloroform is 0.5%.

[0129] The performance of the prepared organic photovoltaic device was tested. The test data are shown in Table 1 under the standard light of the AM1.5 solar simulator.

[0130] Table 1

[0131] As can be seen from Table 1, the devices in Examples 1-10 have better photoelectric conversion efficiency than the device in Comparative Example 1. The reason is that the compound described in this application is used as a third component in the PM6:BTP-eC9 binary system, which broadens the absorption spectrum range of the photoactive layer and improves the light-harvesting ability; it further optimizes the vertical phase separation of the photoactive layer, effectively promoting the generation, transport and collection of charge carriers.

[0132] Device Example 11 The preparation method of device example 11 is the same as that of device example 1, except that the preparation method of the photoactive layer material solution is different, specifically: The photoactive layer material solution is prepared by dissolving the donor material and the acceptor material in chloroform to obtain the photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer PBQx-TF, the acceptor material is selected from compound (22), and the solid additive is selected from DIB. PBQx-TF:compound (22) is added to the chloroform solution at a mass ratio of 1:1.2, with a total concentration of 11 mg / mL, and the volume ratio of DIB in the chloroform is 5 mg / mL.

[0133] Device Example 12 The preparation method of device example 12 is the same as that of device example 1, except that the preparation method of the photoactive layer material solution is different, specifically: The photoactive layer material solution is prepared by dissolving the donor material and the acceptor material in chloroform to obtain the photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer PBQx-TF, the acceptor material is selected from compound (26), and the solid additive is selected from DIB. PBQx-TF:compound (26) is added to the chloroform solution at a mass ratio of 1:1.2, with a total concentration of 11 mg / mL, and the volume ratio of DIB in the chloroform is 5 mg / mL.

[0134] Device Comparison Example 2 The preparation method of device comparative example 2 is the same as that of device example 1, the difference being the preparation method of the photoactive layer material solution, specifically: The method for preparing the photoactive layer material solution is as follows: The donor material and the acceptor material are dissolved in chloroform to obtain the photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer PBQx-TF, the acceptor material is selected from compound IT-4F, and the solid additive is selected from DIB. PBQx-TF:IT-4F is added to the chloroform solution at a mass ratio of 1:1.2, with a total concentration of 11 mg / mL, and the volume ratio of DIB in the chloroform is 5 mg / mL.

[0135] The performance of the prepared organic photovoltaic device was tested. The test data are shown in Table 2 under the standard light of the AM1.5 solar simulator.

[0136] Table 2

[0137] As can be seen from Table 2, Device Example 10 and Device Example 11 have better photoelectric conversion efficiency than Device Comparative Example 2. The reason is that the compound described in this application exhibits an absorption spectrum that is more compatible with sunlight in the photoactive layer, better solubility, and better film morphology compared to IT-4F, thus achieving superior performance.

[0138] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A fused heterocyclic organic compound, characterized in that, The fused heterocyclic organic compound has a structure as shown in general formula (I): （I） in: Selected from any of the following groups: Each time R1 and R2 appear, they are independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl groups having 1-10 carbon atoms, alkoxy groups having 1-10 carbon atoms, or alkylthio groups having 1-10 carbon atoms. * indicates a connection point; Ar1 is selected from substituted or unsubstituted heteroaromatic groups having 10-50 ring atoms; The term "substituted or unsubstituted" indicates that the defined group is not substituted, or is substituted by one or more substituents R, wherein each substituent R is independently selected from: -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl having 1-30 carbon atoms, alkoxy having 1-30 carbon atoms, alkylthio having 1-30 carbon atoms, ester having 1-30 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a combination of at least two of these.

2. The fused heterocyclic organic compound according to claim 1, characterized in that, The fused heterocyclic organic compounds have structures as shown in general formulas (II-1), (II-2), or (II-3): 。 3. The fused heterocyclic organic compound according to claim 2, characterized in that, Each occurrence of R1 and R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-6 carbon atoms, branched alkyl with 3-6 carbon atoms, straight-chain alkoxy with 1-6 carbon atoms, branched alkoxy with 3-6 carbon atoms, straight-chain alkylthio with 1-6 carbon atoms, or branched alkylthio with 3-6 carbon atoms; And / or, the Ar1 is selected from substituted or unsubstituted heteroaromatic groups having 10-40 ring atoms; the heteroatoms in the heteroaromatic group are selected from N, O, S or Se.

4. The fused heterocyclic organic compound according to claim 3, characterized in that, The Ar1 is selected from (B-1) or (B-2): in: Ar2 is selected from R a Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; Each time Ar3 and Ar4 appear, they are selected independently. or ; Each time Z appears, it is independently selected from O, S, or Se; Each time R3 and R4 appear, they are independently selected from the list of R. b Substituted or unsubstituted straight-chain alkyl groups having 1-30 carbon atoms, subject to R b Substituted or unsubstituted branched alkyl groups having 3-30 carbon atoms, R c Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or R c Aromatic groups having 6-10 carbon atoms, substituted or unsubstituted; Each time R5 appears, it is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl groups having 1-10 carbon atoms, or alkoxy groups having 1-10 carbon atoms; Each time R6 appears, it is independently selected from -H, -D, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, or branched alkylthio with 3-20 carbon atoms; R a R c Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-20 carbon atoms, branched-chain alkyl with 3-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, branched-chain alkoxy with 3-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched-chain alkylthio with 3-20 carbon atoms, ester group with 1 to 20 carbon atoms, aromatic group with 6-20 carbon atoms, and heteroaromatic group with 5-20 cyclic atoms. R b Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, aromatic groups having 6-20 carbon atoms, and heteroaromatic groups having 5-20 ring atoms; # indicates a fusion site, which is selected from carbon atoms.

5. The fused heterocyclic organic compound according to claim 4, characterized in that, The (B-1) is selected from the following structures: ; The (B-2) is selected from any of the following structures: 。 6. The fused heterocyclic organic compound according to claim 4 or 5, characterized in that, The Ar2 is selected from any of the following groups: in: Each time X appears, it is independently selected from CR7 or N; Y is selected from O, S, or Se; Each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl groups having 1-20 carbon atoms, branched-chain alkyl groups having 3-20 carbon atoms, cycloalkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched-chain alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched-chain alkylthio groups having 3-20 carbon atoms, ester groups having 1-20 carbon atoms, and R. d Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, and R d One or a combination of at least two of the following heteroaromatic groups, substituted or unsubstituted, having 5-20 ring atoms; the R d Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-20 carbon atoms, or branched alkyl with 3-20 carbon atoms.

7. The fused heterocyclic organic compound according to claim 4 or 5, characterized in that, Each occurrence of R3 is independently selected from the R... b Substituted or unsubstituted straight-chain alkyl groups having 6-20 carbon atoms, by R b Branched alkyl groups having 6-20 carbon atoms, substituted or unsubstituted; Wherein, the R b Each time it appears, it is independently selected from R. e Substituted or unsubstituted phenyl, R e Substituted or unsubstituted thiophene group; the R e Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, straight-chain alkoxy with 1-10 carbon atoms, or branched alkoxy with 3-10 carbon atoms. And / or, each occurrence of R4 is independently selected from the R... b Substituted or unsubstituted straight-chain alkyl groups having 1-20 carbon atoms, subject to R b Substituted or unsubstituted branched alkyl groups having 3-20 carbon atoms, R c Substituted or unsubstituted phenyl groups; Wherein, the R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, straight-chain alkyl with 1-20 carbon atoms, and branched-chain alkyl with 3-20 carbon atoms; And / or, each occurrence of R5 is independently selected from -H, -D, -F, -Cl, -CN, -CF3, straight-chain alkyl with 1-10 carbon atoms, or branched alkyl with 3-10 carbon atoms; And / or, each time R6 appears, it is independently selected from -H, -D, a straight-chain alkyl group having 1-16 carbon atoms, a branched alkyl group having 3-16 carbon atoms, a cycloalkyl group having 3-16 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a branched alkoxy group having 3-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, or a branched alkylthio group having 3-16 carbon atoms.

8. The fused heterocyclic organic compound according to claim 1, characterized in that, The fused heterocyclic organic compound is selected from any of the following structures: 。 9. An end base, characterized in that, The end base is selected from the structure shown in general formula (III): (III) Wherein: R8 is selected independently each time it appears from -H, -D, -F, -Cl, -Br, -I, -CN, -NO2, -CF3, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, or alkylthio with 1-10 carbon atoms.

10. A mixture, characterized in that, The mixture comprises a fused heterocyclic organic compound as described in any one of claims 1-8.

11. An organic photovoltaic device, characterized in that, The organic photovoltaic device comprises a cathode, an anode, and a photoactive layer located between the cathode and the anode, the photoactive layer comprising a fused heterocyclic organic compound as described in any one of claims 1-8 or a mixture as described in claim 10.

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