Trimer acceptor material and application thereof

Abstract

The invention relates to the field of organic photovoltaic materials, in particular to a trimer acceptor material and application thereof. The invention develops a trimer acceptor material as shown in the general formula (I), the shoulder position of the middle NFA unit is connected with the ends of the NFA units on the two sides, so that the trimer acceptor material has proper spectral absorption and three-dimensional stacking conformation, and a relatively complete end structure is reserved. When being used as an acceptor material to be matched with a proper donor material, the blended membrane has more compact and ordered molecular accumulation, and better charge dissociation and transmission are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic photovoltaic materials, and in particular to a kind of trimer acceptor material and its application. BACKGROUND

[0002] Organic photovoltaic (OPV) is expected to be applied in emerging fields such as smart internet of things, smart home, building photovoltaic and vehicle photovoltaic due to its advantages such as flexibility, light weight and low cost solution processability. As a new green energy technology, organic photovoltaic shows a broad application prospect and is an important supplement to traditional silicon-based photovoltaic. At present, the active layer of organic photovoltaic device usually adopts bulk heterojunction (BHJ) composed of p-type electron donor material and n-type electron acceptor material. According to the chemical structure type, the acceptor material can be divided into fullerene acceptor and non-fullerene acceptor. In the early stage of the development of organic photovoltaic technology, fullerene derivatives were widely used due to their high electron affinity, excellent charge transport characteristics and easy to control phase separation morphology when blended with donor materials. Representative materials include [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) and indene double addition fullerene derivative (ICBA). However, the fullerene acceptor material has defects such as unadjustable energy level, weak absorption capacity in visible-near infrared region and poor morphology stability, which greatly limits the further development of this system.

[0003] With the rapid development of non-fullerene acceptor materials, the photoelectric conversion efficiency (PCE) of OPV has been continuously improved. Non-fullerene acceptor materials can be mainly divided into two categories: small molecule acceptors and polymer acceptors. Benefiting from strong absorption characteristics and adjustable energy level, the PCE of OPV devices based on small molecule acceptors has achieved rapid development, but due to the small molecular size, the glass transition temperature is not high, and under external stress (such as light and heat), the acceptor molecules in the active layer are easy to migrate and form uncontrollable metastable morphology, which further leads to serious device performance roll-off. Compared with the small molecule acceptor, the polymer acceptor has a longer molecular backbone, not only has a high glass transition temperature and is not easy to recrystallize or phase separate, but also has excellent mechanical properties and flexibility, so that the active layer is more likely to form a nanometer inter-transmission network structure, which improves the charge transport and stabilizes the device performance. However, the development of polymer acceptors is hindered due to the disadvantages such as poor batch repeatability, relatively low electron mobility, difficulty in adjusting the morphology of active layer and low energy conversion efficiency.

[0004] Oligomeric acceptors in organic photovoltaic devices are a material system between small molecule acceptors and polymer acceptors, usually composed of a defined, repeating unit of a conjugated backbone (e.g. 2-8 units), which has the following advantages: 1. defined and precise molecular structure, significantly improving batch-to-batch reproducibility, and realizing high-purity separation; 2. excellent morphological stability, the degree of molecular diffusion and phase separation is much lower than that of small molecule acceptors under thermal stress or light, significantly improving the long-term stability of the device; 3. flexible molecular design strategy, which can precisely regulate its photoelectric properties by adjusting the number of repeating units, end groups and side chains. Despite the outstanding advantages, oligomeric acceptors still face the following challenges: synthesis efficiency, the multi-step synthesis yield needs to be further improved; morphology optimization, the blending phase separation scale of the donor / oligomeric acceptor needs to be finely controlled; charge recombination inhibition, the interface energy level needs to be optimized to reduce energy loss. Limited by the number and types of oligomeric acceptors, the efficiency of organic photovoltaic cells of oligomeric acceptors is relatively lagging behind, therefore, developing new oligomeric acceptor materials is of great importance to promote the development of organic photovoltaic technology. SUMMARY

[0005] Therefore, the purpose of the present application is to develop a novel trimer acceptor material with a new connection mode, so as to have better spectral absorption and intermolecular stacking, thereby realizing high-efficiency photoelectric conversion efficiency when it is applied as an acceptor material in an organic photovoltaic device.

[0006] The technical scheme of the present application is as follows: A trimer acceptor material has a structure as shown in general formula (I):

[0007] wherein: Ar1, Ar2, Ar3 are independently selected from substituted or unsubstituted heteroaromatic groups with 20-50 ring atoms; Ar4, Ar5, Ar6, Ar7, Ar8, Ar9 are independently selected from substituted or unsubstituted aromatic groups with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups with 5-20 ring atoms; the connection unit L is independently selected from a single bond or at each occurrence; R1 is independently selected from alkyl groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkynyl groups with 2-10 carbon atoms, alkoxy groups with 1-10 carbon atoms, alkylthio groups with 1-10 carbon atoms, substituted or unsubstituted aromatic groups with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups with 5-20 ring atoms; m is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; # indicates the connection site between L and Ar1, Ar4, and Ar5; The term "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from one or more of the following: deuterium (-D), halogen, cyano, 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.

[0008] In a preferred embodiment, the Ar1 is selected from group (A):

[0009] Wherein: Z is selected independently from O, S or Se each time it appears; Each time R2 appears, it is independently selected from alkyl groups having 1-30 carbon atoms; Ar 10 Independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; Indicates the connection site with the double bond.

[0010] In an alternative embodiment, the Ar 10 Independently selected from R a Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R a Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; wherein R a Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, cyano, -CF3, alkyl having 1-10 carbon atoms, alkoxy having 1-10 carbon atoms, alkylthio having 1-10 carbon atoms, aromatic group having 6-10 carbon atoms, or heteroaromatic group having 5-10 cyclic atoms.

[0011] Preferably, the R a Each occurrence is independently selected from methyl (-CH3), -F, -Cl, -Br, cyano, or -CF3.

[0012] Furthermore, the Ar 10 Independently selected from R a Substituted or unsubstituted aromatic groups having 6-10 carbon atoms, or those modified by R a A heteroaromatic group, substituted or unsubstituted, having 5-10 ring atoms.

[0013] In a specific embodiment, Ar1is selected from the group consisting of structures shown in formula (A-1) or (A-2):

[0014] wherein: Y is selected from O, S, or Se; and r is selected from 0, 1, 2, 3, or 4.

[0015] Further, each occurrence of R2is independently selected from a branched alkyl group having 8 to 30 carbon atoms.

[0016] Further, each occurrence of R2is independently selected from a branched alkyl group having 8 to 30 carbon atoms.

[0017] In a specific embodiment, each occurrence of R2is independently selected from or ; wherein * indicates the point of attachment.

[0018] In a specific embodiment, Z is selected from S or Se.

[0019] In a specific embodiment, R a is independently selected from -F or -Cl.

[0020] In an alternative embodiment, Ar2, Ar3are independently selected from group (B):

[0021] wherein: each occurrence of Z1is independently selected from O, S, or Se; each occurrence of R3is independently selected from an alkyl group having 1 to 30 carbon atoms; each occurrence of R4is independently selected from -H, -D, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 5 to 20 ring atoms, or a combination of one or more thereof; Ar 11 is independently selected from a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms.

[0022] In an alternative embodiment, Ar 11 is independently selected from a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms. b b ​substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms. b each occurrence is independently selected from one or a combination of -D, -F, -Cl, -Br, -I, cyano, -CF3, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 10 carbon atoms, aromatic group having 6 to 10 carbon atoms, or heteroaromatic group having 5 to 10 ring atoms.

[0023] Preferably, the R b each occurrence is independently selected from methyl, -F, -Cl, -Br, cyano, or -CF3.

[0024] Further, the Ar 11 is independently selected from a group of R b substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R b substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms.

[0025] In a specific embodiment, the Ar2, Ar3is independently selected from a group of (B-1) or (B-2):

[0026] wherein: Y1is selected from O, S or Se; g is selected from 0, 1, 2, 3 or 4.

[0027] In a specific embodiment, the R b each occurrence is independently selected from methyl, -F, or -Cl.

[0028] Further, the R3each occurrence is independently selected from a branched alkyl group having 8 to 30 carbon atoms.

[0029] Still further, the R3each occurrence is independently selected from a branched alkyl group having 12 to 30 carbon atoms.

[0030] In a specific embodiment, the R3each occurrence is independently selected from or .

[0031] In a specific embodiment, the Z1is selected from S or Se.

[0032] In a specific embodiment, the Y1is selected from S or Se.

[0033] In an alternative embodiment, each occurrence of R4is independently selected from -H, -D, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkylthio group having from 1 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, an alkynyl group having from 2 to 20 carbon atoms, an aromatic group having from 6 to 10 carbon atoms, or a heteroaromatic group having from 5 to 10 ring atoms, or a combination of one or more of these groups.

[0034] Further, each occurrence of R4is independently selected from -H, -D, or any of the following groups, but not limited thereto: .

[0035] In an alternative embodiment, Ar1is selected from group (A-1), and Ar2, Ar3are selected from group (B-1) or (B-2).

[0036] In an alternative embodiment, Ar1is selected from group (A-2), and Ar2, Ar3are selected from group (B-1) or (B-2).

[0037] In a particular embodiment, Ar1is selected from group (A-1), and Ar2, Ar3are selected from group (B-1).

[0038] In a particular embodiment, Ar1is selected from group (A-1), and Ar2, Ar3are selected from group (B-2).

[0039] In a particular embodiment, Ar1is selected from group (A-2), and Ar2, Ar3are selected from group (B-1).

[0040] In a particular embodiment, Ar1is selected from group (A-2), and Ar2, Ar3are selected from group (B-2).

[0041] In a particular embodiment, Ar2, Ar3are selected from the same group.

[0042] In an alternative embodiment, each occurrence of L is independently selected from a single bond, a vinyl group, an ethynyl group, or the following group:

[0043] wherein: x1is selected from 1, 2, 3, 4, or 5; L1is selected from or ; x2 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; x3 is selected from 2, 3, 4, or 5; R5is, at each occurrence, independently selected from -H, -D, -F, -Cl, cyano, -CF3, alkyl of 1-10 carbon atoms, alkoxy of 1-10 carbon atoms, or alkylthio of 1-10 carbon atoms.

[0044] Further, each occurrence of L is independently selected from a single bond or any of the following groups: .

[0045] In a specific embodiment, each occurrence of L is selected from the same group.

[0046] In an alternative embodiment, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9are independently selected from a group consisting of R c substituted or unsubstituted aryl group having 6-10 carbon atoms, or R c substituted or unsubstituted heteroaryl group having 5-10 ring atoms; each occurrence of R c is independently selected from -D, -F, -Cl, -Br, -I, cyano, -CF3, alkyl of 1-10 carbon atoms, alkoxy of 1-10 carbon atoms, alkylthio of 1-10 carbon atoms, aryl of 6-10 carbon atoms, or heteroaryl of 5-10 ring atoms, or a combination of one or more thereof.

[0047] In an alternative embodiment, each occurrence of R is independently selected from or , and q is selected from 0, 1, 2, or 3.

[0048] In a specific embodiment, each occurrence of R is independently selected from , or .

[0049] In an alternative embodiment, each occurrence of R is independently selected from a group consisting of: ; wherein: each occurrence of R6is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, -CF3, alkyl of 1-10 carbon atoms, alkoxy of 1-10 carbon atoms, or alkylthio of 1-10 carbon atoms.

[0050] In a particular embodiment, R6is, at each occurrence, independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, -CF3, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, or methoxy.

[0051] Further, R6is, at each occurrence, independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, -CF3, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, or methoxy. is independently selected from any one of the following groups: .

[0052] In a particular embodiment, R6is, at each occurrence, independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, -CF3, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, or methoxy. is selected from any one of the following structural units, but is not limited thereto: .

[0053] In a particular embodiment, R6is, at each occurrence, independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, -CF3, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, or methoxy. and is selected from any one of the following structural units, but is not limited thereto: .

[0054] In a particular embodiment, the trimeric receptor material according to the present application is selected from the following structures, but is not limited thereto:

[0055] The present application further relates to a mixture comprising a trimeric receptor material as described above.

[0056] Further, the mixture according to the present application further comprises an active layer donor material.

[0057] Preferably, the active layer donor material is selected from polymeric donor materials. The polymeric donor materials can be selected from polythiophene material systems such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymeric material systems such as PF8BT, etc.; novel structure narrow band gap polymeric material systems such as benzo dithiophene (BDT), benzo thiadiazole (BT, BBT), quinoxaline (QU, PQ), pyrazine (TP, PQ) and electron-rich groups (such as thiophene derivatives) copolymerized, such as PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PB2, PCE10, etc., but not limited thereto.

[0058] The present application further relates to a composition comprising the trimer acceptor material as described above or the mixture as described above, and at least one organic solvent.

[0059] The organic solvent is selected from, but not limited to, one or a mixture of two or more of tetralin, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decaline, 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, 1,1,1-trichlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-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, hexamethylphosphoramide.

[0060] The present application further relates to an organic photovoltaic device comprising a cathode, an anode and a photoactive layer between the cathode and the anode, the photoactive layer comprising the trimer acceptor material as described above or the mixture, or prepared from the composition as described above.

[0061] In one embodiment, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material, the photoactive layer acceptor material comprising the trimer acceptor material as described above.

[0062] Further, the photoactive layer donor material is a polymer donor material. The polymer donor material can be selected from a polythiophene material system such as P3AT, P3HT, P3OT, P3DDT, etc.; a fluorene-containing polymer material system such as PF8BT, etc.; a novel structure narrow-bandgap polymer material system such as benzo-dithiophene (BDT), benzo-thiadiazole (BT, BBT), quinoxaline (QU, PQ), pyrazine (TP, PQ), and electron-rich groups (such as thiophene derivatives) copolymerized, such as PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PB2, PCE10, etc., but not limited thereto. For the selection of the active layer donor material, reference can also be made to the literature: Chem. Rev. 2022, 122, 18, 14180-14274.

[0063] The preparation method of the photoactive layer material solution is to dissolve the photoactive layer donor material and the acceptor material in an organic solvent in a certain mass ratio, stir uniformly and sufficiently to dissolve to obtain a photoactive layer solution. The description of the organic solvent is the same as described above.

[0064] The above solution is used to prepare the photoactive layer by a printing or coating preparation method. The printing or coating preparation method can be, but is not limited to, inkjet printing, gravure printing, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roller printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing, pad printing, slit extrusion coating, etc. The preferred ones are slit coating, spin coating and inkjet printing.

[0065] The mass ratio of the photoactive layer donor material and the acceptor material in the organic solvent is preferably 1:0.8-1:1.5; further, the mass ratio of the photoactive layer donor material and the acceptor material in the organic solvent is preferably 1:1-1:1.5; the mass ratio of the photoactive layer donor material and the acceptor material in the organic solvent is preferably 1:1-1:1.2.

[0066] 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.

[0067] Further, the photoactive layer material solution can further include additives for adjusting viscosity, adjusting film forming properties, improving adhesion, etc. The additives can be selected from, but 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 not limited thereto.

[0068] At least one of the anode and the cathode is transparent or semi-transparent 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, etc.; conductive nanomaterials such as metal nanowires, nanoparticle paste, graphene, carbon nanotubes, etc.; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers such as PEDOT:PSS, polypyrrole, and polyaniline, etc.; or materials having a multi-layer structure such as LiF / Al, Li2O / Al, LiF / Fe, MoO3 / Al, Al / Li, Al / BaF2, and Al / BaF2 / Ba, etc., but not limited thereto. In an embodiment, the organic photovoltaic device comprises an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked in sequence, wherein the photoactive layer comprises the trimer acceptor material as described above or the mixture as described above.

[0069] 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 (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; and can also be a polymer material such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited thereto.

[0070] The anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoO x ), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO x , preferably, x is selected from 2 or 3), small molecule self-assembly materials such as 2PACz, MeO-2PACz, etc., but not limited thereto.

[0071] It should be noted that in order to improve the performance of the organic photovoltaic device, the organic photovoltaic device can further comprise other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0072] Further, the organic photovoltaic device further comprises a substrate. In one embodiment, the substrate is disposed on the side of the anode and away from the photoactive layer. In another embodiment, the substrate is disposed on the side of the cathode and away from the photoactive layer.

[0073] In one embodiment, as the substrate, a substrate having excellent transparency, surface smoothness, ease of handling, and water resistance can be used. Specifically, a glass substrate, a thin film glass substrate, or a transparent plastic substrate can be used. The plastic substrate can include a film in a single layer or a multi-layer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), polyimide (PI), Parylene, etc., but is not limited thereto, and a substrate commonly used for organic solar cells can also be used.

[0074] The organic photovoltaic device according to the present application is mainly used in the fields of indoor photovoltaic, wearable devices, smart internet of things, smart home, smart agriculture, building photovoltaic, new energy vehicles, etc.

[0075] Advantages of the present application: The present application develops a kind of trimer acceptor material as general formula (I), by the shoulder position of intermediate NFA unit and the end of two sides NFA unit are connected, it has suitable spectral absorption and three-dimensional packing conformation, and retains relatively complete end structure.As acceptor material and suitable donor material collocation, blend film has more closely and orderly molecular packing, realizes better charge dissociation and transport, so that binary organic photovoltaic device photoelectric conversion efficiency is more than 18%. BRIEF DESCRIPTION OF DRAWINGS

[0076] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the specific embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0077] Figure 1 Structure schematic diagram of the organic photovoltaic device embodiment of the present application. DETAILED DESCRIPTION

[0078] In order to make the purpose, technical scheme and effect of the present application more clear and explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and not to limit the present application. Based on the described embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0079] The selection range of the terms "and / or", "or / and", "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, which includes 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 / or", it should be understood that in the present application, the technical scheme undoubtedly includes the technical scheme connected by "logical and", and also undoubtedly includes the technical scheme connected by "logical or". For example, "A and / or B" includes three parallel schemes of A, B and A+B. For another example, the technical scheme of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C and D (i.e. the technical scheme connected by "logical or"), and also includes any and all combinations of A, B, C and D, i.e. includes the combination of any two or any three of A, B, C and D, and also includes the four-item combination of A, B, C and D (i.e. the technical scheme connected by "logical and").

[0080] In the present application, organic photovoltaic device, organic solar cell, OPV, OSC have the same meaning and can be interchangeable.

[0081] In the present application, photoactive layer, active layer have the same meaning and can be interchangeable.

[0082] In the present application, when the same group contains multiple substituents with the same symbol, each substituent can be the same or different from each other, for example The six R on the benzene ring can be the same or different from each other.

[0083] In the present application, "substituted" means that one or more hydrogen atoms in the substituent is replaced by the substituent.

[0084] In the present application, the "number of ring atoms" means the number of atoms among atoms constituting a ring itself of a structural compound (e.g., monocyclic compound, fused ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound) obtained by bonding atoms into a ring. When the ring is substituted with a substituent, atoms included in the substituent are not included in the ring-forming atoms. The same is true for the "number of ring atoms" described below, unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of quinoline is 10, the number of ring atoms of a thienyl group is 5, and the number of ring atoms of a thienothiophene is 8.

[0085] In the present application, the "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aromatic group can be a monocyclic aromatic group, a fused ring aromatic group, two or more monocyclic aromatic groups connected by a carbon-carbon bond in conjugation, a monocyclic aromatic group and a fused ring aromatic group connected by a carbon-carbon bond in conjugation, two or more fused ring aromatic groups connected by a carbon-carbon bond in conjugation. That is, unless otherwise specified, two or more aromatic groups connected by a carbon-carbon bond in conjugation can also be considered as the aromatic group of the present application. Preferably, the aromatic group is selected from aromatic groups having 6 to 20 C atoms; further, the aromatic group is selected from aromatic groups having 6 to 10 C atoms; the aromatic group includes but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthene, and derivatives thereof.

[0086] In the present application, "heteroaromatic group" refers to a heteroaromatic ring or its derivative comprising 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The term "heteroaromatic group" used herein also includes a group in which one or more heteroaromatic groups are fused with one or more aromatic, aliphatic or heterocyclic rings. Preferably, the heteroaromatic group is selected from a group having 5 to 20 ring atoms; further, selected from a group having 5 to 10 ring atoms. The heteroaromatic group includes, but is not limited to, thienyl, furanyl, pyrrolyl, dioxazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furanopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, perylenyl, phenanthridinyl, perimidinyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, phenoxazinyl and derivatives thereof.

[0087] In the present application, the alkyl group comprises linear alkyl group, branched alkyl group, cyclic alkyl group and combinations thereof, the number of carbon atoms of the linear 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 of the branched alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. The number of carbon atoms of the cyclic alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of linear alkyl groups include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), n-pentyl (-C5H 11 ), n-hexyl (-C6H 13 ), n-heptyl (-C7H 15 ), n-octyl (-C8H 17 ), n-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 C atoms, branched alkyl groups containing 5 C atoms, branched alkyl groups containing 6 C atoms, branched alkyl groups containing 7 C atoms, branched alkyl groups containing 8 C atoms, branched alkyl groups containing 9 C atoms, branched alkyl groups containing 10 C atoms, branched alkyl groups containing 11 C atoms, branched alkyl groups containing 12 C atoms, branched alkyl groups containing 13 C atoms, branched alkyl groups containing 14 C atoms, branched alkyl groups containing 15 C atoms, branched alkyl groups containing 16 C atoms. Non-limiting examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like.

[0088] The term "alkoxy" refers to a group of structure "-O-alkyl", i.e., an alkyl group as defined above attached to another group through an oxygen atom. The straight chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from straight chain alkyl groups, wherein the number of carbon atoms of the straight chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched alkoxy group means that the alkyl group in "-O-alkyl" is selected from branched alkyl groups, wherein the number of carbon atoms of the branched alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0089] The term "alkylthio" refers to a group of structure "-S-alkyl", i.e., an alkyl group as defined above attached to another group through a sulfur atom. The straight chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from straight chain alkyl groups, wherein the number of carbon atoms of the straight chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched alkylthio group means that the alkyl group in "-S-alkyl" is selected from branched alkyl groups, wherein the number of carbon atoms of the branched alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0090] In the present application, when the connecting site in a group is not specified, it means that any optional connecting site in the group is used as the connecting site.

[0091] In the present application, when one or more groups are "independently selected from", it means that when one or more groups appear simultaneously and at multiple places in a compound, they are all independently selected, which can be the same or different.

[0092] In the present application, a single bond to which a substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any optional position of the ring, for example R is connected to any substitutable position of the phenyl ring.

[0093] In the description of structural elements of the present application, the words "comprising" or "including" and the like used in the present application mean that the devices or materials appearing before the word are inclusive of the devices or materials listed after the word and equivalents thereof, and do not exclude other devices or materials.

[0094] In the description of the present application, it should be understood that the terms "upper", "lower", "between layers" and the like 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 the organic solar cell device is placed, or the orientation or positional relationship commonly understood by those skilled in the art, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application.

[0095] In the present application, "combinations thereof", "any combination thereof", "any combination manner thereof", "combinations" and the like include all suitable combination manners of any two, any three or more of the listed groups.

[0096] In the present application, "further", "still further", "in particular" and the like are used for description purposes to indicate differences in content, but should not be understood as a limitation on the scope of protection of the present application.

[0097] In the present application, "optionally", "optional" and "optional" mean optional, i.e. selected from either of the two parallel schemes "have" or "have not". If there are multiple "optional" in a technical solution, and there is no special description, and there is no contradiction or mutual restriction relationship, each "optional" is independent.

[0098] In the present application, the technical features described in an open manner include both closed technical solutions consisting of listed features and open technical solutions containing listed features.

[0099] Synthesis example of trimer receptor material The following examples facilitate better understanding of the disclosure of the present application, and are not intended to make any limitation. The experimental methods used in the following examples are conventional methods, and the materials, reagents and the like used are conventional technologies, which can be obtained from commercial channels, unless otherwise specified.

[0100] Synthesis example 1: synthesis of compound (33)

[0101] Synthesis of compound 1-2: Compound 1-1 (3.4 g, 3.4 mmol) was dissolved in tetrahydrofuran (30 mL), N-bromosuccinimide (1.33 g, 7.48 mmol) was added in portions, and the reaction was stirred at room temperature for 12 h; saturated brine and dichloromethane were added and extracted 3 times, the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure; the crude product was purified by silica gel column chromatography, eluent was PE:DCM = 1:2 (volume ratio), to obtain solid compound 1-2 (3.31 g, 84.2%). MADLI-TOF-MS: 1156.89.

[0102] Synthesis of compound 1-3: Compound 1-2 (2.9 g, 2.5 mmol) was dissolved in anhydrous tetrahydrofuran (30 mL) under a nitrogen atmosphere, 2M lithium diisopropylamide (LDA, 5.0 mL, 10 mmol) was slowly added dropwise at -78 ℃, and the reaction was stirred for 1 h, then moved to room temperature and reacted for 5 h; then the reaction liquid was cooled to -30 ℃, and a mixed solvent of DMF:THF = 1:3 (volume ratio) (total 12 mL) was slowly added dropwise, and moved to room temperature and reacted for 10 min; the reaction liquid was poured into water, and ethyl acetate was added and extracted 3 times, the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure; the crude product was purified by silica gel column chromatography, eluent was PE:DCM = 1:3 (volume ratio), to obtain solid compound 1-3 (2.23 g, 73.5%). MADLI-TOF-MS: 1213.10.

[0103] Synthesis of compound M-1: Compound 1-3 (1.21 g, 1.0 mmol) and 5,6-difluoro-3-(dicyanomethylene)indolinone (1.15 g, 5.0 mmol) were dissolved in chloroform (50 mL) under a nitrogen atmosphere, 5 mL of pyridine was added, and heated to reflux for 12 h. The reaction was cooled to room temperature, the mixture was poured into methanol to precipitate the solid, the solid was suction filtered, and purified by silica gel column chromatography, eluent was PE:DCM = 1:3 (volume ratio), the obtained product was recrystallized with methanol for 2 times, and finally compound M-1 (1.28 g, 78.2%) was obtained. MADLI-TOF-MS: 1637.53.

[0104] Synthesis of compound 33-2: Compound 33-1 (2.8 g, 2.0 mmol), 5,6-difluoro-3-(dicyanomethylene)indan-1-one (460 mg, 2.0 mmol) and 5-bromo-3-(dicyanomethylene)indan-1-one (546 mg, 2.0 mmol) were dissolved in chloroform (100 mL) under nitrogen atmosphere, 10 mL of pyridine was added, and the reaction was heated to reflux for 12 h; the reaction was cooled to room temperature, and the mixture was poured into methanol to precipitate the solid, which was suction filtered, and then purified by silica gel column chromatography using PE:DCM = 1:3 (volume ratio) as eluent. The obtained solid was recrystallized from methanol twice to obtain compound 33-2 (1.42 g, 38.2%). MADLI-TOF-MS: 1859.25.

[0105] Synthesis of compound (33): Compound M-1 (131 mg, 0.08 mmol), hexabutylditin (174 mg, 0.3 mmol), compound 33-2 (372 mg, 0.2 mmol) and Pd(PPh3)4(4.6 mg, 0.004 mmol) were dissolved in toluene (15 mL) under nitrogen atmosphere, and the reaction was heated to 110 °C to reflux for 5 h; the reaction was cooled to room temperature, and then KF solution was added to continue stirring for 20 min, after which the insoluble solid was filtered off by suction filtration, and the liquid phase was poured into methanol to precipitate the solid, which was suction filtered, and then purified by silica gel column chromatography using PE:DCM = 1:4 (volume ratio) as eluent. The obtained product was recrystallized from methanol twice to obtain compound (33) (138 mg, 34.2%). MADLI-TOF-MS: 5036.98.

[0106] Synthesis Example 2: Synthesis of compound (38)

[0107] Synthesis of compound 38-1: Compound 33-1 (0.7 g, 0.5 mmol), 2-(6,7-difluoro-3-oxo-2,3-dihydro-1H- cyclopenta[b]naphthalen-1-yl)propanedinitrile (140 mg, 0.5 mmol) and 2-(6-bromo-3- oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylethyl)propanedinitrile (162 mg, 0.5 mmol) were dissolved in chloroform (20 mL) under nitrogen atmosphere, 2 mL of pyridine was added, and the reaction was heated to reflux for 12 h. The reaction was cooled to room temperature, and the mixture was poured into methanol to precipitate the solid, which was suction filtered and purified by silica gel column chromatography with PE:DCM = 1:3 (volume ratio) as eluent. The obtained solid was recrystallized with methanol for 2 times to obtain compound 38-1 (331 mg, 33.8%). MADLI-TOF-MS: 1959.49.

[0108] Synthesis of compound (38): Compound M-1 (66 mg, 0.04 mmol), dibutyltin (87 mg, 0.15 mmol), compound 38-1 (196 mg, 0.1 mmol) and Pd(PPh3)4 (2.3 mg, 0.002 mmol) were dissolved in toluene (8 mL) under nitrogen atmosphere, and the reaction was heated to 110 °C to reflux for 5 h; the subsequent synthesis reaction steps refer to the synthesis route of compound (33), and finally compound (38) (79 mg, 37.6%) was obtained. MADLI-TOF-MS: 5237.24.

[0109] Synthesis Example 3: Synthesis of compound (47)

[0110] Synthesis of compound 47-2: Compound 47-1 (1.56 g, 2.0 mmol), 1-bromo-2-octyldodecane (2.17 g, 6.0 mmol) and potassium carbonate (1.66 g, 12.0 mmol) were dissolved in N,N-dimethylformamide (DMF, 20 mL) under nitrogen atmosphere, and the reaction was heated to 90 °C for 18 h; cooled to room temperature, the reaction liquid was poured into water, and the aqueous phase was extracted with dichloromethane for 3 times, and the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure; the crude product was purified by silica gel column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain solid compound 47-2 (2.05 g, 76.4%). MADLI-TOF-MS: 1341.02.

[0111] Synthesis of compound 47-3: Compound 47-2 (1.88 g, 1.4 mmol) was dissolved in 1,2-dichloroethane (15 mL) under nitrogen atmosphere, anhydrous POCl3(4.5 mL) and DMF (30 mL) were added, after reaction at room temperature for 6 hours, the reaction was heated to 90 °C, and stirred overnight. The reaction solution was slowly added into ice water, and extracted with ethyl acetate. The organic phase was dried with anhydrous Na2SO4, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography, eluent was PE:DCM = 1:2 (volume ratio), to obtain solid compound 47-3 (1.19 g, 60.9%). MADLI-TOF-MS: 1396.43.

[0112] Synthesis of compound 47-4: Compound 47-3 (977 mg, 0.7 mmol) and 5,6-difluoro-3-(dicyanomethylene)indan-1-one (161 mg, 0.7 mmol) and 5-bromo-3-(dicyanomethylene)indan-1-one (191 mg, 0.7 mmol) were dissolved in chloroform (40 mL) under nitrogen atmosphere, 4 mL of pyridine was added, and heated to reflux for 12 h; the subsequent synthesis reaction steps refer to the synthesis route of compound (33-2), to obtain solid compound 47-4 (524 mg, 40.2%). MADLI-TOF-MS: 1863.77.

[0113] Synthesis of compound (47): Compound M-1 (131 mg, 0.08 mmol), hexabutylditin (174 mg, 0.3 mmol), compound 47-4 (373 mg, 0.2 mmol) and Pd(PPh3)4(4.6 mg, 0.004 mmol) were dissolved in toluene (15 mL) under nitrogen atmosphere, and heated to 110 °C to reflux for 5 h; the subsequent synthesis reaction steps refer to the synthesis route of compound (33), to finally obtain compound (47) (147 mg, 36.4%). MADLI-TOF-MS: 5045.13.

[0114] Synthesis Example 4: Synthesis of compound (48)

[0115] Compound M-1 (131 mg, 0.08 mmol), 2,5-bis(trimethylstannyl)thiophene (123 mg, 0.3 mmol), compound 33-2 (372 mg, 0.2 mmol), Pd2(dba)3(1.84 mg, 0.002 mmol) and P-(o-tol)3(5.0 mg, 0.008 mmol) were dissolved in toluene (15 mL) under nitrogen atmosphere, and the reaction was heated to 110 °C for 12 h. The reaction was cooled to room temperature, and then KF solution was added. After stirring for 20 min, the insoluble solid was filtered off, and the liquid phase was poured into methanol to precipitate the solid. The solid was filtered off, and purified by silica gel column chromatography using PE:DCM = 1:3 (volume ratio) as the eluent. The obtained product was recrystallized twice with methanol, and finally compound (48) (155 mg, 37.2%) was obtained. MADLI-TOF-MS: 5201.75.

[0116] Synthesis Example 5: Synthesis of compound (51)

[0117] Compound M-1 (131 mg, 0.08 mmol), 1,4-bis(5-(trimethylstannyl)thiophen-2-yl)butane (164 mg, 0.3 mmol), compound 33-2 (372 mg, 0.2 mmol), Pd2(dba)3(1.84 mg, 0.002 mmol) and P-(o-tol)3(5.0 mg, 0.008 mmol) were dissolved in toluene (15 mL) under nitrogen atmosphere, and the reaction was heated to 110 °C for 12 h. The subsequent synthesis reaction steps refer to the synthesis route of compound (48), and finally compound (51) (138 mg, 31.5%) was obtained. MADLI-TOF-MS: 5478.22.

[0118] Synthesis Example 6: Synthesis of compound (59)

[0119] Synthesis of compound M-2: Compound 1-3 (607 mg, 0.5 mmol) and 5,6-dichloro-3-(dicyanomethylene)indolin-1-one (658 mg, 2.5 mmol) were dissolved in chloroform (20 mL) under nitrogen atmosphere, and 2 mL of pyridine was added. The reaction was heated to reflux for 12 h. The subsequent synthesis reaction steps refer to the synthesis route of compound (M-1), and compound M-2 (642 mg, 75.4%) was obtained. MADLI-TOF-MS: 1703.47.

[0120] Synthesis of compound 59-1: Compound 33-1 (1.4 g, 1.0 mmol), 5,6-dichloro-3-(dicyanomethylene)indan-1-one (263 mg, 1.0 mmol) and 5-bromo-3-(dicyanomethylene)indan-1-one (273 mg, 1.0 mmol) were dissolved in chloroform (50 mL) under nitrogen atmosphere, 5 mL of pyridine was added, heated to reflux for 12 h; the subsequent synthetic reaction steps refer to the synthetic route of compound (33-2), to obtain compound 59-1 (681 mg, 36.0%). MADLI-TOF-MS: 1892.17.

[0121] Synthesis of compound (59): Compound M-2 (136 mg, 0.08 mmol), 2,5-bis(trimethylstannyl)thiophene (123 mg, 0.3 mmol), compound 59-1 (378 mg, 0.2 mmol), Pd2(dba)3 (1.84 mg, 0.002 mmol) and P-(o-tol)3 (5.0 mg, 0.008 mmol) were dissolved in toluene (15 mL) under nitrogen atmosphere, heated to 110°C and refluxed for 12 h; the subsequent synthetic reaction steps refer to the synthetic route of compound (48), to finally obtain compound (59) (155 mg, 36.3%). MADLI-TOF-MS: 5332.86.

[0122] Synthesis Example 7: Synthesis of compound (128)

[0123] Synthesis of compound 128-2: Compound 128-1 (1.77 g, 2.0 mmol) was dissolved in anhydrous THF (20 mL) under nitrogen atmosphere, a solution of LiAlH4 (20.0 mL, 20.0 mmol) with a concentration of 1M was slowly added, heated to reflux and stirred overnight. Cooled to room temperature, the mixture was slowly added to ice water, and extracted with dichloromethane. The organic phase was dried without Na2SO4, concentrated under reduced pressure to obtain the crude product; the crude product was dissolved in chloroform (20 mL), 2,3-dichloro-5,6-dicyano-p-benzoquinone (4.54 g, 20.0 mmol) and 4,5-difluorobenzene-1,2-diamine (375 mg, 2.6 mmol) were added in turn, stirred at room temperature for 12 h, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography to obtain compound 128-2 (1.39 g, 71.8%). MS: 967.73.

[0124] Synthesis of compound 128-3: Compound 128-2 (1.35 g, 1.4 mmol) was dissolved in tetrahydrofuran (30 mL), N-bromosuccinimide (552 mg, 3.1 mmol) was added in portions, and the reaction was stirred at room temperature for 12 h; the subsequent synthesis reaction steps refer to the synthetic route of compound (1-2), to obtain compound 128-3 (1.19 g, 75.6 %). MADLI-TOF-MS: 1124.65.

[0125] Synthesis of compound 128-4: Compound 128-3 (1.1 g, 1.0 mmol) was dissolved in anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, 2M LDA (2.0 mL, 4 mmol) was slowly added dropwise at -78 ℃, and the reaction was stirred for 1 h, then moved to room temperature for 5 h; the subsequent synthesis reaction steps refer to the synthetic route of compound (1-3), to obtain compound 128-4 (845 mg, 71.5 %). MADLI-TOF-MS: 1181.47.

[0126] Synthesis of compound M-3: Compound 128-4 (236 mg, 0.2 mmol) and 5,6-difluoro-3-(dicyanomethylene)indanone (230 mg, 1.0 mmol) were dissolved in chloroform (10 mL) under a nitrogen atmosphere, 1 mL of pyridine was added, and heated to reflux for 12 h; the subsequent synthesis reaction steps refer to the synthetic route of compound (M-1), to obtain compound M-3 (256 mg, 79.7 %). MADLI-TOF-MS: 1605.08.

[0127] Synthesis of compound (128): Compound M-3 (128 mg, 0.08 mmol), 2,5-bis(trimethylstannyl)thiophene (123 mg, 0.3 mmol), compound 33-2 (372 mg, 0.2 mmol), Pd2(dba)3 (1.84 mg, 0.002 mmol), and P-(o-tol)3 (5.0 mg, 0.008 mmol) were dissolved in toluene (15 mL) under a nitrogen atmosphere, and the reaction was heated to 110 ℃ and refluxed for 12 h; the subsequent synthesis reaction steps refer to the synthetic route of compound (48), to obtain compound (128) (139 mg, 33.6 %). MADLI-TOF-MS: 5169.12.

[0128] Synthesis Example 8: Synthesis of compound (136)

[0129] Synthesis of compound 136-2: Compound 136-2 (1.83 g, 70.2%) was obtained by following the subsequent synthetic reaction steps described in the synthetic route of compound (128-2) from compound 136-1 (2.45 g, 2.0 mmol) dissolved in anhydrous THF (20 mL) under nitrogen atmosphere, slowly adding a solution of LiAlH4(20.0 mL, 20.0 mmol) at a concentration of 1 M, heating to reflux and stirring overnight; MADLI-TOF-MS: 1303.69.

[0130] Synthesis of compound 136-3: Compound 136-3 (1.14 g, 64.5%) was obtained by following the subsequent synthetic reaction steps described in the synthetic route of compound (47-3) from compound 136-2 (1.70 g, 1.3 mmol) dissolved in 1,2-dichloroethane (15 mL) under nitrogen atmosphere, adding anhydrous POCl3(4.5 mL) and DMF (30 mL); MADLI-TOF-MS: 1360.23.

[0131] Synthesis of compound 136-4: Compound 136-4 (367 mg, 40.2%) was obtained by following the subsequent synthetic reaction steps described in the synthetic route of compound (33-2) from compound 136-3 (680 mg, 0.5 mmol), 5,6-difluoro-3-(dicyanomethylene)indanone (115 mg, 0.5 mmol) and 5-bromo-3-(dicyanomethylene)indanone (136 mg, 0.5 mmol) dissolved in chloroform (20 mL) under nitrogen atmosphere, adding 10 mL of pyridine, heating to reflux for 12 h; MADLI-TOF-MS: 1827.50.

[0132] Synthesis of compound (136): Compound (136) (133 mg, 32.6%) was obtained by following the subsequent synthetic reaction steps described in the synthetic route of compound (48) from compound M-3 (128 mg, 0.08 mmol), 2,5-bis(trimethylstannyl)thiophene (123 mg, 0.3 mmol), compound 136-4 (365 mg, 0.2 mmol), Pd2(dba)3(1.84 mg, 0.002 mmol) and P-(o-tol)3(5.0 mg, 0.008 mmol) dissolved in toluene (15 mL) under nitrogen atmosphere, heating to 110 °C and refluxing for 12 h; MADLI-TOF-MS: 5104.98.

[0133] Synthesis Example 9: Synthesis of Compound (138)

[0134] Under a nitrogen atmosphere, compounds M-1 (131 mg, 0.08 mmol), 1,4-bis((5-(trimethylstanyl)thiophen-2-yl)thio)butane (184 mg, 0.3 mmol), compound 59-1 (379 mg, 0.2 mmol), Pd2(dba)3 (1.84 mg, 0.002 mmol), and P-(o-tol)3 (5.0 mg, 0.008 mmol) were dissolved in toluene (15 mL) and refluxed at 110 °C for 12 h. Subsequent synthetic steps followed the synthetic route of compound (48), finally yielding compound (138) (130 mg, 28.6%). MADLI-TOF-MS: 5672.10.

[0135] Organic photovoltaic (OPV) device fabrication examples Device Example 1 Device structure such as Figure 1 As shown, the organic photovoltaic device includes a substrate, an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked sequentially; wherein, the materials of the anode, anode buffer layer, photoactive layer, cathode buffer layer, and cathode are, in sequence: indium tin oxide (ITO) / PEDOT:PSS / photoactive layer material / PDINN / Ag.

[0136] Its preparation method includes the following steps: 1) ITO substrate cleaning 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.

[0137] 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.

[0138] 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 preparation method of the photoactive layer material solution is: dissolving the donor material and the acceptor material in chloroform, and adding a liquid additive 1-chloronaphthalene to obtain a photoactive layer material solution. The donor material in the photoactive layer material solution is selected from a polymer PM6, and the acceptor material is selected from compound (33); PM6: compound (33) is added to the chloroform solution at a mass ratio of 1:1.2, the total concentration is 15 mg / mL, and the amount of 1-chloronaphthalene additive is 0.5% (v:v, volume ratio).

[0139] 4) Preparation of cathode buffer layer The device prepared with the photoactive layer is heat annealed at a hot stage of 100°C for 10 min, and then the cathode buffer layer material PDINN (PDINN is dissolved in methanol to prepare a solution with a concentration of 1.0 mg / mL) is uniformly spin-coated on the photoactive layer at a rotation speed of 3000 rpm for 30 s to obtain the cathode buffer layer.

[0140] 5) Preparation of cathode layer Ag is evaporated on the cathode buffer layer in a high vacuum (1×10 -6 millibar) to form a cathode layer with a thickness of about 100 nm.

[0141] 6) Packaging The device is packaged with a UV-hardening curing resin in a nitrogen glove box.

[0142] Device examples 2-9 The preparation method of device examples 2-9 is the same as that of device example 1, and the difference is that the acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (33) is replaced by compound (38), compound (47), compound (48), compound (51), compound (59), compound (128), compound (136) and compound (138), respectively. See Table 1 for details.

[0143] Device comparative example 1 The preparation method of device comparative example 1 is the same as that of device example 1, and the difference is that the acceptor material compound (33) is replaced by compound Ref(1), which has the following structure:

[0144] The prepared organic photovoltaic devices are tested for performance. Under the irradiation of a solar simulator AM1.5 standard light, the test device data of device examples 1-9 and device comparative example 1 are shown in Table 1.

[0145] Table 1

[0146] From the data in Table 1, it can be seen that when the trimer molecule of the application is used as a receptor material in combination with a suitable donor material in an organic photovoltaic device, it exhibits good photoelectric conversion efficiency. In particular, device embodiment 2, device embodiment 4, device embodiment 5, device embodiment 6, device embodiment 7 and device embodiment 8 exhibit a photoelectric conversion efficiency of more than 18.5%, which is much higher than that of device comparative embodiment 1, indicating that the introduction of a connecting unit on the shoulder position to prepare a trimer receptor molecule has a significant advantage in optimizing the energy level, improving the morphology and regulating the molecular packing.

[0147] Obviously, the above examples are merely examples for the sake of clarity, and are not limiting of the embodiments. For those of ordinary skill in the art, other different forms of changes or variations can also be made on the basis of the above description. All the embodiments do not need to be exhausted here. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A trimer receptor material, characterized in that, The trimer acceptor material has a structure as shown in general formula (I): in: Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted heteroaromatic groups having 20-50 ring atoms; Ar4, Ar5, Ar6, Ar7, Ar8, and Ar9 are independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms. Each time the connecting unit L appears, it is independently selected from a single key or... ; Each time R1 appears, it is independently selected from alkyl groups having 1-10 carbon atoms, alkenyl groups having 2-10 carbon atoms, alkynyl groups having 2-10 carbon atoms, alkoxy groups having 1-10 carbon atoms, alkylthio groups having 1-10 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms. m is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; # indicates the connection site between L and Ar1, Ar4, and Ar5; The term "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, halogen, cyano, 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 trimer acceptor material according to claim 1, characterized in that, The Ar1 is selected from the group (A): in: Each time Z appears, it is independently selected from O, S, or Se; Each time R2 appears, it is independently selected from alkyl groups having 1-30 carbon atoms; Ar 10 Independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; Indicates the connection site with the double bond; Preferably, the Ar 10 Independently selected from R a Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R a Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; Among them, R a Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, cyano, -CF3, alkyl having 1-10 carbon atoms, alkoxy having 1-10 carbon atoms, alkylthio having 1-10 carbon atoms, aromatic group having 6-10 carbon atoms, or heteroaromatic group having 5-10 cyclic atoms.

3. The trimer acceptor material according to claim 2, characterized in that, The Ar1 is selected from the structure shown in formula (A-1) or (A-2): in: Y is selected from O, S, or Se; r can be selected from 0, 1, 2, 3 or 4.

4. The trimer acceptor material according to claim 1, characterized in that, The Ar2 and Ar3 are independently selected from group (B): in: Each time Z1 appears, it is independently selected from O, S, or Se; Each time R3 appears, it is independently selected from alkyl groups having 1-30 carbon atoms; Each time R4 appears, it is independently selected from one or a combination of at least two of the following: hydrogen, -D, alkyl group having 1-30 carbon atoms, alkoxy group having 1-30 carbon atoms, alkathio group having 1-30 carbon atoms, alkenyl group having 2-30 carbon atoms, alkynyl group having 2-30 carbon atoms, aromatic group having 6-20 carbon atoms, or heteroaromatic group having 5-20 cyclic atoms. Ar 11 Independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; Preferably, the Ar 11 Independently selected from R b Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R b Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; wherein R b Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, -I, cyano, -CF3, alkyl having 1-10 carbon atoms, alkoxy having 1-10 carbon atoms, alkylthio having 1-10 carbon atoms, aromatic group having 6-10 carbon atoms, or heteroaromatic group having 5-10 cyclic atoms.

5. The trimer acceptor material according to claim 4, characterized in that, Ar2 and Ar3 are independently selected from groups (B-1) or (B-2): in: Y1 is selected from O, S, or Se; g is selected from 0, 1, 2, 3 or 4.

6. The trimer acceptor material according to claim 1, characterized in that, Each occurrence of L is independently selected from single bonds, vinyl groups, ethynyl groups, or any of the following groups: in: x1 is selected from 1, 2, 3, 4 or 5; L1 is selected from or * indicates a connection site; x2 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; x3 is selected from 2, 3, 4, or 5; Each time R5 appears, it is independently selected from -D, -F, -Cl, cyano, -CF3, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, or alkylthio with 1-10 carbon atoms. Preferably, each occurrence of L is independently selected from a single bond or any of the following groups: 。 7. The trimer acceptor material according to claim 1, characterized in that, The Ar4, Ar5, Ar6, Ar7, Ar8, and Ar9 are independently selected from those of R. c Substituted or unsubstituted aromatic groups having 6-10 carbon atoms, or those modified by R c Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms; the R c Each occurrence is independently selected from one or a combination of at least two of the following: -D, -F, -Cl, -Br, -I, cyano, -CF3, alkyl having 1-10 carbon atoms, alkoxy having 1-10 carbon atoms, alkylthio having 1-10 carbon atoms, aromatic group having 6-10 carbon atoms, or heteroaromatic group having 5-10 ring atoms. Preferably, the Independently selected or The q is selected from 0, 1, 2 or 3; Preferably, the Independently selected from the following groups: ； Wherein: R6 is selected independently each time it appears from -H, -D, -F, -Cl, -Br, -I, cyano, -CF3, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, or alkylthio with 1-10 carbon atoms.

8. The trimer acceptor material according to any one of claims 1-7, characterized in that, The Selected from any of the following structural units: ； Preferably, the and Independently selected from any of the following structural units: 。 9. A mixture, characterized in that, The mixture comprises the trimer acceptor material as described in any one of claims 1-8.

10. An organic photovoltaic device, characterized in that, The organic photovoltaic device includes a cathode, an anode, and a photoactive layer located between the cathode and the anode, the photoactive layer comprising a trimer acceptor material as described in any one of claims 1-8 or a mixture as described in claim 9.

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