Dimeric non-fullerene organic compound and application thereof

Abstract

The invention relates to the field of organic photovoltaic materials, in particular to a dimeric non-fullerene organic compound and application thereof. The invention develops a dimeric non-fullerene organic compound shown as a general formula (I), and the dimeric non-fullerene organic compound as an acceptor material has excellent photoelectric conversion performance when being applied to an indoor weak light condition by limiting a terminal group and a connection mode between two monomers.

Description

Technical Field

[0001] This invention relates to the field of organic photovoltaic materials, specifically to a dimer nonfullerene organic compound and its applications. Background Technology

[0002] Organic photovoltaic (OPV) cells, due to their tunable spectrum, lightweight, flexibility, and solution-processable properties, are considered the next generation of photovoltaic technology and have received widespread attention from academia and industry. In recent years, the development of small-molecule acceptor structures with acceptor-donor-acceptor (ADA) structures has driven rapid advancements in the photoelectric conversion efficiency (PCE) of single-junction OPVs. However, based on previous research, device performance degradation is mainly caused by the diffusion behavior of small-molecule acceptors during the evolution of the blended film from a kinetic equilibrium state to a thermodynamic equilibrium state. Therefore, increasing the molecular size of the acceptor material to reduce the molecular diffusion coefficient, such as developing dimers, trimers, or even polymer acceptors, is an effective strategy for constructing devices with both stability and high efficiency. Polymer acceptor materials currently face problems of batch-to-batch variability in synthesis and severe chain entanglement. Oligomeric small-molecule acceptors can combine the advantages of small-molecule and polymer acceptors, including well-defined molecular structures, high glass transition temperatures, and low diffusion rates, thereby achieving better device efficiency and stability. Therefore, developing suitable oligomeric small-molecule acceptors is crucial for the development of OPV technology.

[0003] Current research on oligomeric small molecule acceptors mainly focuses on the selection of linking groups and linkage methods. Linking groups can be electron-donating (or electron-withdrawing) groups, or rigid (or flexible) groups, and linkage methods include end-to-end, wing-to-wing, and core-to-core connections. The choice of different linking groups and linkage methods has a substantial impact on molecular configuration, aggregation behavior, and charge transport properties, and a universal structure-property relationship has not yet been established. Furthermore, the development of oligomeric small molecule acceptor materials is primarily based on standard sunlight conditions, with limited reports on materials developed for indoor conditions. Therefore, there is an urgent need to develop oligomeric small molecule acceptor materials suitable for indoor applications, which is crucial for promoting the commercialization of organic photovoltaics in indoor environments. Summary of the Invention

[0004] Based on this, the purpose of this invention is to develop a dimer nonfullerene organic compound, thereby developing an oligomer acceptor material suitable for indoor photovoltaics by limiting the selection of end groups of the nonfullerene acceptor material monomers and the connection mode between the two monomers.

[0005] The technical solution of this invention is as follows:

[0006] A dimer nonfullerene organic compound having a structure as shown in general formula (I):

[0007]

[0008] in:

[0009] Y is selected from O, S, or Se;

[0010] Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, alkylthio with 1-30 carbon atoms, or ester with 1-30 carbon atoms; the two R1s may be cyclic or acyclic;

[0011] Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6-50 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-50 ring atoms.

[0012] Each occurrence of m is independently selected from 0 or 1;

[0013] Each time R2 appears, it is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, or alkylthio with 1-30 carbon atoms;

[0014] 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, -CF3, -CN, nitro, alkyl having 1-30 carbon atoms, alkenyl having 2-30 carbon atoms, alkynyl having 2-30 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, or heteroaromatic group having 5-20 cyclic atoms, or a combination of at least two of these.

[0015] In an alternative embodiment, the dimer nonfullerene organic compound has a structure as shown in general formula (II-1), (II-2), or (II-3):

[0016]

[0017] .

[0018] In one alternative embodiment, Y is selected from S or Se.

[0019] In an optional embodiment, each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, alkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkylthio having 1-20 carbon atoms, and ester having 1-20 carbon atoms; the two R1s may be cyclic or acyclic with each other.

[0020] In a specific embodiment, each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, straight-chain alkyl with 1-10 carbon atoms, branched-chain alkyl with 3-10 carbon atoms, straight-chain alkoxy with 1-10 carbon atoms, branched-chain alkoxy with 3-10 carbon atoms, straight-chain alkylthio with 1-10 carbon atoms, branched-chain alkylthio with 3-10 carbon atoms, and ester with 1-10 carbon atoms; the two R1s may be cyclic or acyclic with each other.

[0021] In an alternative embodiment, each occurrence of R1 is independently selected from -H, -D, -F, -Cl, a straight-chain alkyl group having 1-10 carbon atoms, or a straight-chain alkoxy group having 1-10 carbon atoms; the two R1s may be cyclic or acyclic with each other.

[0022] In a specific embodiment, when the two R1s form a loop, the... Selected from , where * indicates a connection site.

[0023] In a particular embodiment, the It can be selected from the following structures, but is not limited to them:

[0024] .

[0025] In an alternative embodiment, each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, straight-chain alkyl having 1-10 carbon atoms, branched-chain alkyl having 3-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, branched-chain alkoxy having 3-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, or branched-chain alkylthio having 3-10 carbon atoms.

[0026] In one specific embodiment, the Choose from any of the following structures, but not limited to:

[0027] .

[0028] In one specific embodiment, the Choose from any of the following structures, but not limited to:

[0029] .

[0030] In an optional embodiment, Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 20-50 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 20-50 ring atoms.

[0031] Furthermore, Ar1 and Ar2 are independently selected from the following groups:

[0032]

[0033] in:

[0034] Each time Z appears, it is independently selected from O, S, or Se;

[0035] Each occurrence of W is independently selected from C or Si;

[0036] Each occurrence of Ar3 is independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms.

[0037] R3, R4, R5, R6, and R7 are each independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, substituted or unsubstituted alkyl groups having 1-30 carbon atoms, substituted or unsubstituted alkoxy groups having 1-30 carbon atoms, substituted or unsubstituted alkylthio groups having 1-30 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms.

[0038] In an alternative embodiment, the Ar3 is independently selected from the following groups:

[0039]

[0040] in:

[0041] Each time V appears, it is independently selected from O, S, or Se;

[0042] R8 is selected independently from one or a combination of at least two of the following groups: -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, straight-chain alkyl with 1-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, substituted or unsubstituted aromatic group with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group with 5-20 ring atoms.

[0043] # indicates a fused ring site, which is selected from C atoms.

[0044] Furthermore, each occurrence of R8 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -CF3, nitro, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, phenyl, and is surrounded by one or more R groups. a Substituted phenyl, thiophene, or substituted with one or more R a Substituted thiophene group, R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, nitro, 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.

[0045] In one specific embodiment, the group (A-1) is independently selected from the following groups:

[0046] .

[0047] In an alternative embodiment, each occurrence of R3 is independently selected from straight-chain or branched alkyl groups having 8-30 carbon atoms.

[0048] Furthermore, each occurrence of R3 is independently selected from any of the following structures, but is not limited to:

[0049] .

[0050] In an optional embodiment, each occurrence of R4 is independently selected from -H, -D, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted alkoxy groups having 1-20 carbon atoms, substituted or unsubstituted alkylthio groups having 1-20 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms.

[0051] In one embodiment, each occurrence of R4 is independently selected from -H, -D, a straight-chain alkyl group having 1-20 carbon atoms, a branched alkyl group having 3-20 carbon atoms, a straight-chain alkoxy group having 1-20 carbon atoms, or a branched alkoxy group having 3-20 carbon atoms.

[0052] In a specific embodiment, each occurrence of R4 is independently selected from any of the following groups:

[0053] .

[0054] In an alternative embodiment, the group (A-2) is independently selected from the following groups:

[0055] .

[0056] In an alternative embodiment, each occurrence of R6 is independently selected from substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted aromatic groups having 6-10 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-10 cyclic atoms.

[0057] Furthermore, each occurrence of R6 is independently selected from the R... b Substituted or unsubstituted alkyl groups having 1-20 carbon atoms, R c Substituted or unsubstituted phenyl, or substituted by R c Substituted or unsubstituted thiophene groups; the R b Selected from R * Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R * Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; R * Each occurrence is independently selected from -D, F, -Cl, -Br, -I, -CN, -CF3, nitro, straight-chain alkyl with 1-10 carbon atoms, or straight-chain alkoxy with 1-10 carbon atoms; R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, nitro, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, or branched alkoxy with 3-20 carbon atoms.

[0058] In a specific embodiment, each occurrence of R6 is independently selected from the R... b Substituted or unsubstituted straight-chain alkyl groups having 6-20 carbon atoms, R b Substituted or unsubstituted branched alkyl groups having 6-20 carbon atoms or .

[0059] Preferably, the R c Each occurrence is independently selected from straight-chain alkyl groups having 1-10 carbon atoms, branched alkyl groups having 3-10 carbon atoms, straight-chain alkoxy groups having 1-10 carbon atoms, or branched alkoxy groups having 3-10 carbon atoms.

[0060] In one specific embodiment, each occurrence of R6 is independently selected from any of the following groups, but is not limited thereto:

[0061] .

[0062] In an alternative embodiment, each occurrence of R5 is independently selected from -H, -D, alkyl groups having 1-20 carbon atoms, or alkoxy groups having 1-20 carbon atoms.

[0063] Furthermore, each occurrence of R5 is independently selected from -H, -D, straight-chain alkyl with 1-12 carbon atoms, straight-chain alkyl with 3-12 carbon atoms, straight-chain alkoxy with 1-12 carbon atoms, or branched-chain alkoxy with 3-12 carbon atoms.

[0064] In one specific embodiment, each occurrence of R5 is independently selected from -H, -D, or any of the following groups, but not limited thereto:

[0065] .

[0066] In one specific embodiment, R5 is selected from the same group.

[0067] In a particular embodiment, each occurrence of R7 is independently selected from -H, -D, -F, -Cl, a straight-chain alkyl group having 1-6 carbon atoms, or a straight-chain alkoxy group having 1-6 carbon atoms.

[0068] In a particular embodiment, each occurrence of R7 is independently selected from -H, -D, -F, -Cl, methyl, or methoxy.

[0069] In one specific embodiment, Ar1 and Ar2 are selected from the same group.

[0070] In one specific embodiment, the dimer nonfullerene organic compound according to this application is selected from any of the following structures, but is not limited thereto:

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] .

[0105] The present invention further relates to a mixture comprising a dimer nonfullerene organic compound as described above.

[0106] Furthermore, the mixture further comprises another organic functional material selected from photoactive layer donor materials and / or photoactive layer acceptor materials.

[0107] 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.

[0108] In one embodiment, the 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, Z8, 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.

[0109] The present invention further relates to a composition comprising the dimer nonfullerene organic compound or mixture as described above, and at least one organic solvent.

[0110] 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, 1,1-trichlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, 1 One or a mixture of two or more of the following: 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.

[0111] Furthermore, the composition 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, 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 thereto.

[0112] The present invention further 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, as described above, a dimer nonfullerene organic compound or mixture, or prepared from the above composition.

[0113] In one embodiment, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material, wherein the photoactive layer acceptor material comprises a dimerized non-fullerene organic compound as described above. The photoactive layer donor material is described as above.

[0114] The method for preparing the photoactive layer material solution is as follows: the photoactive layer donor material and acceptor material are dissolved in an organic solvent at a certain mass ratio, and the mixture is stirred until fully dissolved to obtain the photoactive layer solution.

[0115] 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.

[0116] The preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:0.8 to 1:1.5; further, the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:1.5; the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:1.2.

[0117] The concentration of the photoactive layer donor material in the organic solvent is preferably 3-15 mg / mL; further, the concentration of the photoactive layer donor material in the organic solvent is preferably 4-10 mg / mL.

[0118] At least one of the anode and cathode is transparent or translucent to facilitate light incidence. The material used to fabricate 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.

[0119] 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 dimer nonfullerene organic compound or mixture as described above.

[0120] 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, Ca, and 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.

[0121] The anode buffer layer material is selected from PEDOT:PSS and molybdenum oxide (MoO). x ), vanadium oxide (V₂O₅), nickel oxide (NiO), 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.

[0122] 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.

[0123] Furthermore, the organic photovoltaic device also includes a substrate. 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.

[0124] 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.

[0125] In a preferred embodiment, the organic photovoltaic device is an indoor organic photovoltaic device.

[0126] Furthermore, the indoor organic photovoltaic devices can be used in fields such as smart IoT and smart homes; specifically, they can be used in products such as electronic nameplates, electronic price tags, and smart door locks.

[0127] This invention develops a dimer nonfullerene organic compound as shown in general formula (I). By defining the end groups and the connection mode between the two monomers, it exhibits excellent photoelectric conversion performance as an acceptor material under indoor low-light conditions. The reason is as follows: Compared to or It possesses relatively weak electron-withdrawing properties, thereby reducing intermolecular charge transfer effects and enabling a blue shift in the absorption spectrum to better match the indoor spectrum. Furthermore, thanks to the optimized molecular structure, the blend film based on the dimer non-fullerene organic compound exhibits a suitable phase separation structure, significantly promoting exciton dissociation and effectively suppressing charge recombination. Therefore, the organic photovoltaic device based on the non-fullerene organic compound ultimately achieves a photoelectric conversion efficiency of nearly 28% under low-light conditions. Attached Figure Description

[0128] 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.

[0129] Figure 1 This is a schematic diagram of an organic photovoltaic device. Detailed Implementation

[0130] 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.

[0131] 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").

[0132] In this invention, organic photovoltaic devices, organic solar cells, OPV, and OSC have the same meaning and can be used interchangeably.

[0133] In this invention, the terms "photoactive layer" and "active layer" have the same meaning and can be used interchangeably.

[0134] 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 Rs on the benzene ring can be the same or different from each other.

[0135] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0136] 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.

[0137] In this invention, "aromatic group" refers to any optional functional group or substituent derived from an aromatic carbide 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 aromatic groups in this application. Preferably, the aromatic group 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, phenanthryl, fluoranthracene, and their derivatives.

[0138] 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 5-20 ring atoms; more preferably, it is selected from those having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to: thiophene, furanyl, pyrrolyl, diazolyl, triazolyl, imidazole, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridineyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrryl, thienopyrryl, thienothiophene, furanol, furanol, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazanaphthyl, phenanthridine, primidyl, quinazolinone, dibenzothiophene, dibenzofuranyl, carbazole, phenazinyl and their derivatives.

[0139] In this invention, the alkyl group comprises straight-chain alkyl, branched-chain alkyl, cyclic alkyl, and combinations thereof. The straight-chain alkyl group may have 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6 carbon atoms. The branched-chain alkyl group may have 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6 carbon atoms. The cyclic alkyl group may have 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6 carbon atoms. 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. Non-limiting examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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 limiting this invention.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] Example of Synthesis of Dimeric Nonfullerene Organic Compounds

[0152] 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.

[0153] Synthesis Example 1: Synthesis of Compound (4)

[0154]

[0155] Synthesis of compound 4-2:

[0156] Compound 4-1 (4.0 g, 2.87 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadien[b]thiophene-4-yl)malononitrile (0.8 g, 2.87 mmol) were accurately weighed and dissolved in 50 mL of anhydrous toluene. 4 mL of boron trifluoride diethyl ether and 4 mL of acetic anhydride were added, and the mixture was stirred at room temperature for 10 min. Methanol was then added to precipitate the solid, which was filtered. The solid was purified by column chromatography using petroleum ether:dichloromethane = 5:1 (v / v) as the eluent, yielding approximately 1.82 g of compound 4-2, with a yield of 38.4%. MALDI-TOF-MS: 1653.51.

[0157] Synthesis of compound 4-3:

[0158] Compound 4-2 (1.5 g, 0.91 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (0.25 g, 1.09 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 2 mL of boron trifluoride diethyl ether and 2 mL of acetic anhydride were added, and the mixture was stirred at room temperature for 10 min. Methanol was added to precipitate the solid, which was then filtered. The solid was purified by column chromatography using petroleum ether:dichloromethane (3:1, v / v). Approximately 1.44 g of compound 4-3 was obtained, with a yield of 84.8%. MALDI-TOF-MS: 1865.91.

[0159] Synthesis of compound (4):

[0160] Accurately weigh compound 4-3 (0.45 g, 0.24 mmol), 2,5-bis(tri-n-butyltin)thiophene (0.07 g, 0.11 mmol), tris(dibenzylindeneacetone)dipalladium (10 mg, 0.01 mmol), and tris(o-methylphenyl)phosphine (20 mg, 0.063 mmol) and add them sequentially to a reaction flask. Add 10 mL of anhydrous toluene, purge with nitrogen for 30 min, and then raise the temperature to 70 °C and stir for two hours. After the starting materials have completely reacted, cool the temperature to room temperature, add methanol to precipitate the solid, and filter. The solid is purified by column chromatography using petroleum ether:dichloromethane = 5:1 (volume ratio) as the eluent. Approximately 267 mg of compound (4) was obtained, with a yield of 66.4%. MALDI-TOF-MS: 3653.55.

[0161] Synthesis Example 2: Synthesis of Compound (6)

[0162]

[0163] The synthesis method of compound (6) is the same as that of compound (4), except that 2,5-bis(tri-n-butyltin)thiophene was replaced with (3,4-dimethoxythiophene-2,5-diyl)bis(trimethyltin) of equimolar molecular weight, to obtain approximately 238 mg of compound (6), with a yield of 58.3%. MALDI-TOF-MS: 3713.28.

[0164] Synthesis Example 3: Synthesis of Compound (7)

[0165]

[0166] The synthesis method of compound (7) is the same as that of compound (4), except that 2,5-bis(tri-n-butyltin)thiophene was replaced with 2,5-bis(tri-butyltin)-3,4-ethylenedioxythiophene of equimolar molecular weight, to obtain approximately 227 mg of compound (6), with a yield of 55.6%. MALDI-TOF-MS: 3711.04.

[0167] Synthesis Example 4: Synthesis of Compound (8)

[0168]

[0169] Synthesis of compound 8-2:

[0170] Compound 8-1 (2.56 g, 2 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadienyl[b]thiophene-4-yl)malononitrile (0.56 g, 2 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 3 mL of boron trifluoride diethyl ether and 3 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. This yielded approximately 1.05 g of compound 8-2, with a yield of 34.1%. MALDI-TOF-MS: 1541.53.

[0171] Synthesis of compound 8-3:

[0172] Compound 8-2 (0.46 g, 0.3 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (83 mg, 0.36 mmol) were accurately weighed and dissolved in 10 mL of anhydrous toluene. 0.5 mL of boron trifluoride diethyl ether and 0.5 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. This yielded approximately 452 mg of compound 8-3, with a yield of 85.9%. MALDI-TOF-MS: 1753.87.

[0173] Synthesis of compound (8):

[0174] The synthesis method of compound (8) is the same as that of compound (4), except that: compound 4-3 is replaced with compound 8-3 of equimolar molecular weight, and compound 2,5-bis(tri-n-butyltin)thiophene is replaced with (3,4-difluorothiophene)bis(trimethyltin) of equimolar molecular weight, to obtain approximately 217 mg of compound (8), with a yield of 56.9%. MALDI-TOF-MS: 3464.88.

[0175] Synthesis Example 5: Synthesis of Compound (12)

[0176]

[0177] Synthesis of compound 12-2:

[0178] Compound 12-1 (1.58 g, 1.07 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadieno[b]thiophene-4-yl)malononitrile (0.3 g, 1.07 mmol) were accurately weighed and dissolved in 20 mL of anhydrous toluene. 1.5 mL of boron trifluoride diethyl ether and 1.5 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. Approximately 593 mg of compound 12-2 was obtained, with a yield of 31.8%. MALDI-TOF-MS: 1741.65.

[0179] Synthesis of compound 12-3:

[0180] Compound 12-2 (0.52 g, 0.3 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (83 mg, 0.36 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 0.5 mL of boron trifluoride diethyl ether and 0.5 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. Approximately 461 mg of compound 12-3 was obtained, with a yield of 78.7%. MALDI-TOF-MS: 1953.72.

[0181] Synthesis of compound (12):

[0182] Compound 12-3 (0.33 g, 0.17 mmol), 2,5-bis(tri-n-butyltin)thiophene (53 mg, 0.08 mmol), tris(dibenzylidene indeneacetone)palladium (8 mg, 0.008 mmol), and tris(o-methylphenyl)phosphine (16 mg, 0.05 mmol) were accurately weighed and added sequentially to a reaction flask. 6 mL of anhydrous toluene was added. The subsequent synthesis reaction was carried out in accordance with the synthesis of compound (4). Approximately 224 mg of compound (12) was obtained, with a yield of 73.1%. MALDI-TOF-MS: 3828.95.

[0183] Synthesis Example 6: Synthesis of Compound (16)

[0184]

[0185] Synthesis of compound 16-2:

[0186] Compound 16-1 (1.5 g, 1.05 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadieno[b]thiophene-4-yl)malononitrile (0.29 g, 1.05 mmol) were accurately weighed and dissolved in 20 mL of anhydrous toluene. 1.5 mL of boron trifluoride diethyl ether and 1.5 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. Approximately 658 mg of compound 16-2 was obtained, with a yield of 37.2%. MALDI-TOF-MS: 1685.48.

[0187] Synthesis of compound 16-3:

[0188] Compound 16-2 (0.5 g, 0.29 mmol) and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (95 mg, 0.36 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 0.5 mL of boron trifluoride diethyl ether and 0.5 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. Approximately 407 mg of compound 16-3 was obtained, with a yield of 72.7%. MALDI-TOF-MS: 1930.61.

[0189] Synthesis of compound (16):

[0190] Accurately weigh compound 16-3 (0.33 g, 0.17 mmol), 2,5-bis(tributyltinyl)-3,4-ethylenedioxythiophene (58 mg, 0.08 mmol), tris(dibenzylidene indeneacetone)dipalladium (8 mg, 0.008 mmol), and tris(o-methylphenyl)phosphine (16 mg, 0.05 mmol) and add them sequentially to a reaction flask. Add 6 mL of anhydrous toluene. The subsequent synthesis reaction is the same as that of compound (4). Approximately 197 mg of compound (16) was obtained, with a yield of 64.1%. MALDI-TOF-MS: 3841.34.

[0191] Synthesis Example 7: Synthesis of Compound (20)

[0192]

[0193] Synthesis of compound 20-2:

[0194] Compound 20-1 (2.17 g, 1.47 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadieno[b]thiophene-4-yl)malononitrile (0.41 g, 1.47 mmol) were accurately weighed and dissolved in 20 mL of anhydrous toluene. 2 mL of boron trifluoride diethyl ether and 2 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. This yielded approximately 1.02 g of compound 20-2, with a yield of 39.9%. MALDI-TOF-MS: 1737.38.

[0195] Synthesis of compound 20-3:

[0196] Compound 20-2 (0.43 g, 0.25 mmol) and 2-(6,7-difluoro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malononitrile (92 mg, 0.33 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 0.4 mL of boron trifluoride diethyl ether and 0.4 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. Approximately 355 mg of compound 20-3 was obtained, with a yield of 71.0%. MALDI-TOF-MS: 1999.63.

[0197] Synthesis of compound (20):

[0198] Compound 28-3 (0.32 g, 0.16 mmol), 2,5-bis(tributyltinyl)-3,4-ethylenedioxythiophene (53 mg, 0.074 mmol), tris(dibenzylidene indeneacetone)dipalladium (8 mg, 0.008 mmol), and tris(o-methylphenyl)phosphine (16 mg, 0.05 mmol) were accurately weighed and added sequentially to a reaction flask. 6 mL of anhydrous toluene was added. The subsequent synthesis reaction was carried out in accordance with the synthesis of compound (4). Approximately 202 mg of compound (20) was obtained, with a yield of 68.6%. MALDI-TOF-MS: 3979.32.

[0199] Synthesis Example 8: Synthesis of Compound (36)

[0200]

[0201] Synthesis of compound 36-2:

[0202] Compound 36-1 (0.45 g, 0.26 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadienyl[b]thiophene-4-yl)malononitrile (73 mg, 0.26 mmol) were accurately weighed and dissolved in 10 mL of anhydrous toluene. 0.4 mL of boron trifluoride diethyl ether and 0.4 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. Approximately 192 mg of compound 36-2 was obtained, with a yield of 37.6%. MALDI-TOF-MS: 1964.58.

[0203] Synthesis of compound 36-3:

[0204] Compound 36-2 (0.18 g, 0.09 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (25 mg, 0.11 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 0.2 mL of boron trifluoride diethyl ether and 0.2 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. Approximately 169 mg of compound 36-3 was obtained, with a yield of 86.3%. MALDI-TOF-MS: 2176.81.

[0205] Synthesis of compound (36):

[0206] Compound 36-3 (0.16 g, 0.074 mmol), 2,5-bis(tri-n-butyltin)thiophene (23 mg, 0.034 mmol), tris(dibenzylidene indeneacetone)palladium (4 mg, 0.004 mmol), and tris(o-methylphenyl)phosphine (8 mg, 0.025 mmol) were accurately weighed and added sequentially to a reaction flask. 5 mL of anhydrous toluene was added. The subsequent synthesis reaction was carried out in accordance with the synthesis of compound (4). Approximately 86 mg of compound (36) was obtained, with a yield of 59.2%. MALDI-TOF-MS: 4275.83.

[0207] Synthesis Example 9: Synthesis of Compound (42)

[0208]

[0209] Synthesis of compound 42-2:

[0210] Compound 42-1 (3.5 g, 2.25 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadieno[b]thiophene-4-yl)malononitrile (0.63 g, 2.25 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 3.5 mL of boron trifluoride diethyl ether and 3.5 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. Approximately 1.48 g of compound 42-2 was obtained, with a yield of 36.2%. MALDI-TOF-MS: 1817.75.

[0211] Synthesis of compound 42-3:

[0212] Compound 42-2 (0.5 g, 0.27 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (76 mg, 0.33 mmol) were accurately weighed and dissolved in 10 mL of anhydrous toluene. 0.5 mL of boron trifluoride diethyl ether and 1 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. Approximately 456 mg of compound 42-3 was obtained, with a yield of 83.2%. MALDI-TOF-MS: 2029.81.

[0213] Synthesis of compound (42):

[0214] Compound 42-3 (0.20 g, 0.10 mmol) and 2,5-bis(tributyltinyl)-3,4-ethylenedioxythiophene (35 mg, 0.049 mmol), tris(dibenzylidene indeneacetone)dipalladium (8 mg, 0.008 mmol), and tris(o-methylphenyl)phosphine (16 mg, 0.05 mmol) were added sequentially to a reaction flask under a nitrogen atmosphere. 10 mL of anhydrous toluene was added to dissolve the compounds. Subsequent synthesis was performed following the method described for compound (4). Approximately 125 mg of compound (42) was obtained, with a yield of 63.1%. MALDI-TOF-MS: 4039.47.

[0215] Synthesis Example 10: Synthesis of Compound (45)

[0216]

[0217] Compound 42-3 (0.20 g, 0.10 mmol) and 2,5-bis(trimethyltinyl)selenophene (22 mg, 0.049 mmol), tris(dibenzylindeneacetone)palladium (8 mg, 0.008 mmol), and tris(o-methylphenyl)phosphine (16 mg, 0.05 mmol) were added sequentially to a reaction flask under a nitrogen atmosphere. 10 mL of anhydrous toluene was added to dissolve the compounds. Subsequent synthesis was performed following the method described for compound (4). Approximately 153 mg of compound (42) was obtained, with a yield of 77.5%. MALDI-TOF-MS: 4028.27.

[0218] Synthesis Example 11: Synthesis of Compound (57)

[0219]

[0220] Synthesis of compound 57-2:

[0221] Compound 57-1 (0.35 g, 0.27 mmol) and 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadien[b]thiophene-4-yl)malononitrile (75 mg, 0.27 mmol) were accurately weighed and dissolved in 10 mL of anhydrous toluene. 0.4 mL of boron trifluoride diethyl ether and 0.4 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-2. Approximately 156 mg of compound 57-2 was obtained, with a yield of 37.0%. MALDI-TOF-MS: 1563.22.

[0222] Synthesis of compound 57-3:

[0223] Compound 57-2 (0.14 g, 0.09 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (25 mg, 0.11 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 0.2 mL of boron trifluoride diethyl ether and 0.2 mL of acetic anhydride were added. The subsequent synthesis was performed following the method described for compound 4-3. Approximately 138 mg of compound 57-3 was obtained, with a yield of 86.3%. MALDI-TOF-MS: 1775.81.

[0224] Synthesis of compound (57):

[0225] Compound 57-3 (0.13 g, 0.074 mmol), 2,5-bis(tri-n-butyltin)thiophene (23 mg, 0.034 mmol), tris(dibenzylindeneacetone)palladium (4 mg, 0.004 mmol), and tris(o-methylphenyl)phosphine (8 mg, 0.025 mmol) were accurately weighed and added sequentially to a reaction flask. 5 mL of anhydrous toluene was added. The subsequent synthesis reaction was carried out in accordance with the synthesis of compound (4). Approximately 86 mg of compound (36) was obtained, with a yield of 72.8%. MALDI-TOF-MS: 3472.50.

[0226] Synthesis Example 12: Synthesis of Compound Ref (1)

[0227]

[0228] Synthesis of compound a:

[0229] Compound 4-2 (0.17 g, 0.1 mmol) and 2-(2-chloro-6-oxo-5,6-dihydro-4H-cyclopentadienyl[b]thiophene-4-yl)malononitrile (28 mg, 0.12 mmol) were accurately weighed and dissolved in 30 mL of anhydrous toluene. 0.2 mL of boron trifluoride diethyl ether and 0.2 mL of acetic anhydride were added. Subsequent synthetic reactions followed the method described for compound 4-3, yielding approximately 147 mg of compound a, with a yield of 78.6%. MALDI-TOF-MS: 1869.86.

[0230] Synthesis of compound Ref(1):

[0231] Compound a (0.14 g, 0.074 mmol), 2,5-bis(tri-n-butyltin)thiophene (23 mg, 0.034 mmol), tris(dibenzylindeneacetone)palladium (4 mg, 0.004 mmol), and tris(o-methylphenyl)phosphine (8 mg, 0.025 mmol) were accurately weighed and added sequentially to a reaction flask. 5 mL of anhydrous toluene was added. The subsequent synthesis reaction was carried out in accordance with the synthesis of compound (4). Approximately 79 mg of compound Ref (1) was obtained, with a yield of 63.4%. MALDI-TOF-MS: 3662.14.

[0232] Organic photovoltaic (OPV) device fabrication examples

[0233] Device Example 1

[0234] Device structure such as Figure 1 As shown, the organic photovoltaic device comprises a substrate, a cathode, a cathode buffer layer, a photoactive layer, an anode buffer layer, and an anode, which are stacked sequentially. Its fabrication method includes the following steps:

[0235] 1) ITO substrate cleaning

[0236] 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.

[0237] 2) Preparation of cathode buffer layer

[0238] A ZnO precursor solution was uniformly spin-coated onto ITO in air and dried on a hot stage at 150°C for 10 min to obtain a cathode buffer layer with a thickness of about 30 nm.

[0239] 3) Preparation of photoactive layer

[0240] In a glove box (inert gas atmosphere), the photoactive layer material solution was uniformly spin-coated onto the cathode buffer layer at a speed of 1800-3000 rpm to obtain a photoactive layer with a total thickness of approximately 110 nm.

[0241] 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 PM7, and the acceptor material is selected from compound (4). PM7:compound (4) is added to the chloroform solution at a mass ratio of 1:1.2, and the total concentration is 16.5 g / mL.

[0242] 4) Preparation of the anode buffer layer

[0243] In high vacuum (1×10) -6 MoO3 is vapor-deposited onto the photoactive layer in millibars to form an anode buffer layer with a thickness of approximately 10 nm.

[0244] 5) Anode layer preparation

[0245] In high vacuum (1×10) -6 Ag is deposited onto the anode buffer layer in millibars to form an anode layer with a thickness of approximately 100 nm.

[0246] 6) Packaging

[0247] The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0248] Device Example 2-11

[0249] The preparation methods of device examples 2-11 are the same as those of device example 1. The difference lies in the selection of the acceptor material in the photoactive layer. Specifically, the acceptor material compound (4) is replaced with compound (6), compound (7), compound (8), compound (12), compound (16), compound (20), compound (36), compound (42), compound (45) and compound (57), respectively. See Table 1 for details.

[0250] Comparative Examples of Devices 1-2

[0251] The preparation methods of the devices in Comparative Examples 1-2 are the same as those in Device Example 1, except that the acceptor material compound (4) is replaced with compound Ref (1) and compound Ref (2). The structure of compound Ref (2) is shown in the figure below:

[0252]

[0253] The prepared organic photovoltaic cell device was tested under indoor light. The cell current-voltage curve was tested under a 3000K LED light source (1000 lux) simulator, and the photoelectric conversion efficiency was calculated, as shown in Table 1.

[0254] Table 1

[0255]

[0256] As shown in Table 1, when the dimer molecule described in this invention is used as an acceptor material in combination with a suitable donor material in organic photovoltaic devices, it exhibits superior indoor photoelectric conversion efficiency. In particular, devices 5 and 6 show a photoelectric conversion efficiency exceeding 27.5%, which is much higher than that of devices 1 and 2 in comparison. This indicates that this application, by limiting the selection of end groups and the connection method of the dimer, enables it to exhibit more suitable energy levels and morphology.

[0257] 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 dimerized non-fullerene organic compound, characterized in that: The dimer nonfullerene organic compound has a structure as shown in general formula (I): in: Y is selected from O, S, or Se; Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, alkylthio with 1-30 carbon atoms, or ester with 1-30 carbon atoms; the two R1s may be cyclic or acyclic; Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6-50 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-50 ring atoms. m is selected from 0 or 1; Each time R2 appears, it is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, or alkylthio with 1-30 carbon 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, -CF3, -CN, nitro, alkyl having 1-30 carbon atoms, alkenyl having 2-30 carbon atoms, alkynyl having 2-30 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, or heteroaromatic group having 5-20 cyclic atoms, or a combination of at least two of these.

2. The dimerized non-fullerene organic compound according to claim 1, characterized in that: The dimer nonfullerene organic compound has a structure as shown in general formula (II-1), (II-2), or (II-3): 。 3. The dimer nonfullerene organic compound according to claim 1 or 2, characterized in that: Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, straight-chain alkyl groups having 1-10 carbon atoms, and straight-chain alkoxy groups having 1-10 carbon atoms. The two R1s may be cyclic or non-cyclic.

4. The dimer nonfullerene organic compound according to claim 1 or 2, characterized in that: The It can be selected from the following structures, but is not limited to them: ； Where: * indicates a connection site.

5. The dimerized nonfullerene organic compound according to claim 1 or 2, characterized in that: The Ar1 and Ar2 are independently selected from the following groups: in: Each time Z appears, it is independently selected from O, S, or Se; Each occurrence of W is independently selected from C or Si; Each occurrence of Ar3 is independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms. R3, R4, R5, R6, and R7 are each independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, substituted or unsubstituted alkyl groups having 1-30 carbon atoms, substituted or unsubstituted alkoxy groups having 1-30 carbon atoms, substituted or unsubstituted alkylthio groups having 1-30 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms.

6. The dimerized non-fullerene organic compound according to claim 5, characterized in that: The Ar3 is independently selected from the following groups: in: Each time V appears, it is independently selected from O, S, or Se; R8 is selected independently from one or a combination of at least two of the following groups: -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, nitro, straight-chain alkyl with 1-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, straight-chain alkylthio with 1-20 carbon atoms, branched or cyclic alkyl with 3-20 carbon atoms, branched or cyclic alkoxy with 3-20 carbon atoms, branched or cyclic alkylthio with 3-20 carbon atoms, substituted or unsubstituted aromatic group with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group with 5-20 ring atoms. # indicates a fused ring site, which is selected from C atoms.

7. The dimer non-fullerene organic compound according to claim 6, characterized in that: The Ar1 and Ar2 are independently selected from the following groups: ; Preferably, each occurrence of R3 is independently selected from a straight-chain alkyl group having 8-30 carbon atoms, or a branched-chain alkyl group having 8-30 carbon atoms; Preferably, each occurrence of R4 is independently selected from -H, -D, a straight-chain alkyl group having 1-20 carbon atoms, a branched alkyl group having 3-20 carbon atoms, a straight-chain alkoxy group having 1-20 carbon atoms, or a branched alkoxy group having 3-20 carbon atoms. Preferably, each occurrence of R5 is independently selected from -H, -D, alkyl groups having 1-20 carbon atoms, or alkoxy groups having 1-20 carbon atoms; Preferably, each occurrence of R6 is independently selected from the R... b Substituted or unsubstituted alkyl groups having 1-20 carbon atoms, R c Substituted or unsubstituted phenyl, or substituted with R c Substituted or unsubstituted thiophene groups; the R b Selected from R * Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R * Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, nitro, straight-chain alkyl with 1-10 carbon atoms, or straight-chain alkoxy with 1-10 carbon atoms; R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, nitro, straight-chain alkyl with 1-20 carbon atoms, branched alkyl with 3-20 carbon atoms, straight-chain alkoxy with 1-20 carbon atoms, or branched alkoxy with 3-20 carbon atoms; Preferably, each occurrence of R7 is independently selected from -H, -D, -F, -Cl, a straight-chain alkyl group having 1-6 carbon atoms, or a straight-chain alkoxy group having 1-6 carbon atoms.

8. The dimerized non-fullerene organic compound according to claim 1, characterized in that: The dimer nonfullerene organic compound is selected from any of the following structures: 。 9. A mixture, characterized in that: The mixture comprises a dimer nonfullerene organic compound as described in any one of claims 1-8.

10. An organic photovoltaic device, the organic photovoltaic device comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, characterized in that: The photoactive layer comprises a dimer nonfullerene organic compound as described in any one of claims 1-8 or a mixture as described in claim 9.

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