Asymmetric dimerization acceptor material as well as preparation method and application thereof

Abstract

The invention discloses an asymmetric dimerization acceptor material as well as a preparation method and application thereof, and belongs to the technical field of organic material chemistry. The dimerization material is shown as a formula I, and two fused ring electron acceptor molecules with different structures are bridged by adopting an aromatic unit. The dimerization material combines the advantages of a small molecule material and a polymer material, not only has good film-forming property and excellent light / heat stability, but also presents a monodisperse molecular structure, and avoids the problem of batch difference. Compared with a dimerization acceptor material with a symmetrical structure, the asymmetric dimerization acceptor material is expected to obtain a higher dielectric constant, and energy level, band gap, crystallinity and intermolecular interaction can be accurately regulated and controlled by selecting small molecules with different structures. A battery device prepared based on the material is expected to have high photoelectric conversion efficiency and stability at the same time. Therefore, the development of the material has important value for promoting the industrialization of organic solar cells. # imgabs0 #

Description

Technical Field

[0001] The present application relates to an asymmetric dimerization receptor material and a preparation method and application thereof, and belongs to the technical field of organic material chemistry. Background Art

[0002] As a low-cost, flexible photovoltaic technology, organic solar cells (OSCs) have attracted extensive attention from academia and industry. In the past few years, thanks to the continuous development of polycyclic small molecule acceptors (SMA) materials, the power conversion efficiency (PCE) of OSCs has exceeded 20%. However, the inherent low glass transition temperature (T g ) and high diffusion characteristics make the microstructure of the corresponding active layer unstable under external stress, which is not conducive to the long-term operation stability of the device. Dimeric receptors are usually connected by two small molecule fragments. Compared with SMA, dimeric receptors have larger molecular size, higher T g And lower diffusion coefficient, these characteristics can stabilize the morphology of the active layer, thereby improving the stability of the corresponding device. In addition, the dimerized receptor also has a clear molecular structure, excellent crystallinity and good film-forming properties. Therefore, solar cell devices prepared using dimerized receptors are expected to achieve both high PCE and stability, which is of great significance for promoting the industrial application of organic photovoltaics.

[0003] Studies have found that compared with symmetric SMA, asymmetric SMA has a higher molecular dipole moment and lower exciton binding energy, which is conducive to enhancing intermolecular interactions, improving electron mobility, and promoting exciton dissociation, thereby improving the photovoltaic performance of solar cell devices. In the past two years, although many dimerization receptor materials have been reported, most of them have symmetrical structures. Considering the potential advantages of asymmetric molecular structures in improving non-fullerene receptors, the development of asymmetric dimerization receptor materials has important research value. However, due to the challenges brought by material synthesis, this type of asymmetric dimerization receptor material has not yet been reported. Summary of the invention

[0004] According to one aspect of the present application, a technical solution for preparing an asymmetric dimerization receptor material is provided, wherein the prepared asymmetric dimerization receptor material has a highly planar molecular structure and exhibits strong light absorption, suitable electronic energy level, low exciton binding energy and high glass transition temperature. Based on such materials, long-term stable and high-efficiency photovoltaic devices can be prepared.

[0005] This application adopts the following technical solutions:

[0006] According to the first aspect of the present application, an asymmetric dimerization receptor material is provided, wherein the asymmetric dimerization receptor material has a structure as described in Formula I;

[0007]

[0008] Wherein, R1, R2, R3, R4 are independently selected from C1 to C 30 Alkyl I, C1~C 30 The halogenated alkyl I, C4~C 20 Aryl I, C4~C 20 The substituted aryl group I has one of the groups shown in formula I-1;

[0009] R'—M—*Formula I-1;

[0010] In formula I-1, R' is selected from C1 to C 30 Alkyl II, C1~C 30 One of the haloalkyl II;

[0011] M is selected from O or S;

[0012] The substituent of the substituted aryl group I is selected from one of alkyl, haloalkyl, alkoxy, haloalkoxy, halogen, alkylthio, and haloalkylthio;

[0013] X1, X2 are independently selected from O, S, Se or Te;

[0014] Ar1, Ar2 are independently selected from C4~C 20 wherein the aryl group contains at least one thiophene ring which forms a condensed ring with the pyrrole ring in formula I;

[0015] EG1, EG2, and EG3 are independently selected from one of the groups having the structure shown in Formula II, wherein the dotted line in Formula II is the double bond connection position;

[0016]

[0017] In formula II, Ar3 is selected from C4~C 40 Aryl II, C4~C 40 Substituted aromatic II, C3~C 40 Heteroaryl, C3~C 40 One of the substituted heteroaryl groups;

[0018] The substituents of the substituted aryl II and the substituted heteroaryl are independently selected from any one of halogen, cyano, haloalkyl, alkyl, alkoxy, alkylthio, ester and carbonyl;

[0019] The π group in formula I is selected from thiophene, One of the groups of the structure shown.

[0020] The material of the structure shown in Formula I of the present application uses an aromatic unit to bridge two condensed ring electron acceptor molecules with different structures. This type of dimerization material combines the advantages of small molecule materials and polymer materials, not only has good film forming properties and excellent light / thermal stability, but also presents a monodisperse molecular structure, avoiding batch variability problems. Compared with the dimerization acceptor material with a symmetrical structure, the asymmetric dimerization acceptor material is expected to obtain a higher dielectric constant, and can accurately control the energy level, band gap, crystallinity and intermolecular interactions by selecting small molecules with different structures. The battery device prepared based on this type of material is expected to have high photoelectric conversion efficiency and stability at the same time. Therefore, the development of this material is of great value to promoting the industrialization of organic solar cells.

[0021] Optionally, the asymmetric dimerization receptor material comprises a small molecule receptor and an intermediate linking group;

[0022] The intermediate connecting group is the π group shown in Formula I, and the small molecule receptor is at least one of the structures connected to both sides of the π group in Formula I.

[0023] Optionally, R1, R2, R3 and R4 are independently selected from C1 to C 28 Straight chain alkoxy, C3~C 30 Branched alkoxy, C1~C 28 Straight chain fluorinated alkoxy, C3~C 30 Branched fluorinated alkoxy, C1~C 28 Straight chain alkylthio, C3~C 30 Branched alkylthio, C1~C 28 Straight chain fluorinated alkylthio, C3~C 30 Branched fluorinated alkylthio, C1~C 28 Straight chain alkyl, C3~C 30 Branched alkyl, C1~C 28 Straight chain fluorinated alkyl, C3~C 30 Branched fluorinated alkyl, C4~C 20 Alkyl aromatic group, C4~C 20 Fluorinated alkyl aromatic groups, C4~C 20 Alkoxy aromatic group, C4~C 20 Fluorinated alkoxy aromatic groups, C4~C 20 Alkylthio aromatic group, C4~C 20 Fluorinated alkylthio aromatic groups, C4~C 20 Aromatic groups, C4~C 20 Any one of the fluorinated aromatic groups.

[0024] Optionally, R1, R2, R3 and R4 are independently selected from C1 to C 20Straight chain alkoxy, C3~C 20 Branched alkoxy, C1~C 20 Straight chain fluorinated alkoxy, C3~C 20 Branched fluorinated alkoxy, C1~C 20 Straight chain alkylthio, C3~C 20 Branched alkylthio, C1~C 20 Straight chain fluorinated alkylthio, C3~C 20 Branched fluorinated alkylthio, C1~C 20 Straight chain alkyl, C3~C 20 Branched alkyl, C1~C 20 Straight chain fluorinated alkyl, C3~C 20 Branched fluorinated alkyl, C4~C 20 Alkyl aromatic group, C4~C 20 Fluorinated alkyl aromatic groups, C4~C 20 Alkoxy aromatic group, C4~C 20 Fluorinated alkoxy aromatic groups, C4~C 20 Alkylthio aromatic group, C4~C 20 Fluorinated alkylthio aromatic groups, C4~C 20 Aromatic groups, C4~C 20 Any one of the fluorinated aromatic groups.

[0025] Optionally, R1, R2, R3 and R4 are independently selected from C1 to C 12 Straight chain alkoxy, C3~C 12 Branched alkoxy, C1~C 12 Straight chain fluorinated alkoxy, C3~C 12 Branched fluorinated alkoxy, C1~C 12 Straight chain alkylthio, C3~C 12 Branched alkylthio, C1~C 12 Straight chain fluorinated alkylthio, C3~C 12 Branched fluorinated alkylthio, C1~C 12 Straight chain alkyl, C3~C 12 Branched alkyl, C1~C 12 Straight chain fluorinated alkyl, C3~C 12 Branched fluorinated alkyl, C4~C 12 Alkyl aromatic group, C4~C 12 Fluorinated alkyl aromatic groups, C4~C 12 Alkoxy aromatic group, C4~C 12 Fluorinated alkoxy aromatic groups, C4~C 12 Alkylthio aromatic group, C4~C 12 Fluorinated alkylthio aromatic groups, C4~C12 Aromatic groups, C4~C 12 Any one of the fluorinated aromatic groups.

[0026] Optionally, Ar1 and Ar2 are independently selected from any one of the groups containing 1 to 5 thiophene rings, and the group containing 1 to 5 thiophene rings may be a substituted or unsubstituted thiophene group, or a substituted or unsubstituted condensed ring formed by 2 to 5 thiophene rings.

[0027] Optionally, Ar3 is selected from C4~C 10 Substituted aromatic II, C3~C 10 One of the substituted heteroaryl groups.

[0028] Optionally, the heteroaryl is a monocyclic heteroaryl.

[0029] Optionally, the heteroaryl group contains 5 skeleton ring atoms, wherein at least one ring atom is a heteroatom, and the heteroatom is selected from a sulfur atom.

[0030] Optionally, EG1 and EG2 are independently selected from one of the structures shown in Formula II-1, Formula II-2, Formula II-3, Formula II-4, Formula II-5, and Formula II-6;

[0031]

[0032] In Formula II-1 to Formula II-6, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 One independently selected from the group consisting of a hydrogen atom, a halogen, a cyano group, a C1-C30 alkyl group III, a C1-C30 alkoxy group I, a C1-C30 alkylthio group I, a C1-C30 ester group I, and a carbonyl group I.

[0033] Optionally, EG1 and EG2 are independently selected from at least one of 5-bromocyanoindanone, 4-fluoro-5-bromocyanoindanone, 4,6-difluoro-5-bromocyanoindanone, 4-chloro-5-bromocyanoindanone and 4,6-dichloro-5-bromocyanoindanone.

[0034] Optionally, EG1 and EG2 are selected from Formula II-1.

[0035] Optionally, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 Any one independently selected from hydrogen, halogen, cyano, haloalkyl, alkyl, alkoxy, alkylthio, ester and carbonyl; wherein the alkyl contained in the alkyl, alkoxy, alkylthio and ester groups are straight-chain or branched alkyl groups with 1 to 30 carbon atoms.

[0036] Optionally, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 Independently selected from a straight chain or branched chain with 1 to 3 carbon atoms; the dotted double bond is the double bond connection position with the nitrogen-containing ladder heterocycle, and the dotted single bond is the single bond connection position with the electron-donating unit.

[0037] Optionally, the halogen is a fluorine atom.

[0038] Optionally, the EG3 is selected from one of the structures shown in Formula II-7, Formula II-8, Formula II-9, Formula II-10, Formula II-11, Formula II-12, Formula II-13, Formula II-14, Formula II-15, Formula II-16, Formula II-17, Formula II-18, and Formula II-19;

[0039]

[0040] In Formula II-7 to Formula II-19, the R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 Independently selected from one of a hydrogen atom, a halogen, a cyano group, a C1-C30 alkyl group IV, a C1-C30 alkoxy group II, a C1-C30 alkylthio group II, a C1-C30 ester group II, and a carbonyl group II.

[0041] Optionally, the EG3 is selected from at least one of 5,6-difluoro-3-(dicyanomethylene)indone, 3-(dicyanomethylene)indone, 5,6-dichloro-3-(dicyanomethylene)indone, 6-fluoro-3-(dicyanomethylene)indone, and 6-chloro-3-(dicyanomethylene)indone.

[0042] Optionally, EG3 is selected from Formula II-7.

[0043] Optionally, the R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 Any one independently selected from hydrogen, halogen, cyano, haloalkyl, alkyl, alkoxy, alkylthio, ester and carbonyl; wherein the alkyl contained in the alkyl, alkoxy, alkylthio and ester groups are straight-chain or branched alkyl groups with 1 to 30 carbon atoms.

[0044] Optionally, the R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 Independently selected from a straight chain or branched chain having 1 to 3 carbon atoms; the dotted double bond is the double bond connection position with the nitrogen-containing ladder-shaped heterocyclic ring.

[0045] Optionally, the halogen is a fluorine atom.

[0046] Optionally, the π group in Formula I is selected from one of the structures shown in Formula III-1, Formula III-2, Formula III-3, Formula III-4, Formula III-5, Formula III-6, Formula III-7, and Formula III-8;

[0047]

[0048] Wherein, X3 is selected from O, S or Se;

[0049] R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 29 , R 30 Any one independently selected from halogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and ester;

[0050] R 28 One selected from C1 to C30 alkyl groups.

[0051] Optionally, the π group in Formula I is selected from one of 2,5-bis(trimethyltin)thiophene, 2,5-bis(trimethyltin)thiophene[3,2-b]thiophene, 5,5′-bis(trimethyltin)-2,2′-bithiophene, (3,3′-difluoro-[2,2′-bithiophene]-5,5′-diyl)bistrimethyltin, and 2,6-bis(trimethyltin)benzo[1,2-b:4,5-b′]bithiophene.

[0052] According to the second aspect of the present application, a method for preparing the above-mentioned asymmetric dimerization receptor material is provided, comprising the following steps:

[0053] (1) reacting a mixture I containing a compound represented by formula IV, a compound represented by formula V, a catalyst I, and a solvent I to obtain a compound represented by formula VI;

[0054] (2) reacting a mixture II containing the compound represented by formula VII, the compound represented by formula VIII, a catalyst I, and a solvent I to obtain a compound represented by formula IX;

[0055] (3) reacting a mixture III containing the compound represented by formula VI, the compound represented by formula X, a catalyst II, and a solvent II in an inert atmosphere to obtain a compound represented by formula XI;

[0056] (4) reacting a mixture IV containing the compound represented by formula IX, the compound represented by formula XI, a catalyst II, and a solvent II in an inert atmosphere to obtain a compound represented by formula XII;

[0057] (5) reacting a mixture V containing the compound represented by formula XII, the EG3 compound, the solvent III, and the catalyst III to obtain an asymmetric dimerization receptor material having a structure represented by formula I;

[0058]

[0059] Optionally, in step (1), the molar ratio of the compound represented by formula IV to the compound represented by formula V is 1:1:(0.8-1.3).

[0060] Optionally, in step (1), the molar ratio of the compound represented by formula IV to the compound represented by formula V is independently selected from any value of 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2 or a range between any two of the above.

[0061] Optionally, in step (1), the catalyst I is acetic anhydride and boron trifluoride etherate.

[0062] Optionally, in step (1), the amount of catalyst I added is 0.5% to 5% of the molar amount of the compound represented by formula IV.

[0063] Optionally, in step (1), the amount of catalyst I added is the molar amount of the compound represented by formula IV independently selected from any value among 0.5%, 1%, 1.5%, 2%, 2.5%, 3.0%, 3.5%, 4%, 4.5%, 5%, or a range between any two of the above.

[0064] Optionally, in step (1), the molar ratio of the acetic anhydride to the boron trifluoride etherate is 1:(0.1-1.2).

[0065] Optionally, in step (1), the solvent I is selected from at least one of toluene, chloroform, chlorobenzene and 1,2-dichloroethane.

[0066] Optionally, in step (1), the ratio of the compound represented by formula IV to the solvent I is 1 mmol: (5-10) mL.

[0067] Optionally, in step (1), the temperature of reaction I is 0 to 50° C., and the time of reaction I is 10 to 60 min.

[0068] Optionally, in step (1), the temperature of the reaction I is independently selected from any value of 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C or a range between any two of the above.

[0069] Optionally, in step (1), the time of reaction I is independently selected from any value among 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min or a range between any two of the above.

[0070] Optionally, in step (1), the temperature of reaction I is 0 to 20° C., and the time of reaction I is 20 to 40 min.

[0071] Optionally, in step (2), the molar ratio of the compound represented by formula VII to the compound represented by formula VIII is 1:(0.8-1.2).

[0072] Optionally, in step (2), the molar ratio of the compound represented by formula VII to the compound represented by formula VIII is independently selected from any value of 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2 or a range between any two of the above.

[0073] Optionally, in step (2), the catalyst I is acetic anhydride and boron trifluoride etherate.

[0074] Optionally, in step (2), the amount of catalyst I added is 0.5% to 5% of the molar amount of the compound represented by formula VII.

[0075] Optionally, in step (2), the amount of catalyst I added is the molar amount of the compound represented by formula VII independently selected from any value among 0.5%, 1%, 1.5%, 2%, 2.5%, 3.0%, 3.5%, 4%, 4.5%, 5% or a range between any two of the above.

[0076] Optionally, in step (2), the molar ratio of the acetic anhydride to the boron trifluoride etherate is 1:(0.1-1.2).

[0077] Optionally, in step (2), the solvent I is selected from at least one of toluene, chloroform, chlorobenzene, and 1,2-dichloroethane.

[0078] Optionally, in step (2), the ratio of the compound represented by formula VII to the solvent I is 1 mmol: (100-150) mL.

[0079] Optionally, in step (2), the temperature of reaction II is 0 to 50° C., and the time of reaction II is 10 to 60 min.

[0080] Optionally, in step (2), the temperature of reaction II is independently selected from any value of 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C or a range between any two of the above.

[0081] Optionally, in step (2), the time of reaction II is independently selected from any value among 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min or a range between any two of the above.

[0082] Optionally, in step (2), the temperature of reaction II is 0 to 20° C., and the time of reaction II is 20 to 40 min.

[0083] Optionally, in step (3), the catalyst II is tris dibenzylideneacetone dipalladium and tri(o-methylphenyl)phosphine.

[0084] Optionally, in step (3), the molar ratio of the compound represented by formula VI: the compound represented by formula X: trisdibenzylideneacetone dipalladium: tri(o-methylphenyl)phosphine is 1:(0.8-1.5):(0.05-0.2):(0.25-0.5).

[0085] Optionally, in step (3), the solvent II is selected from at least one of toluene, chloroform, chlorobenzene and 1,2-dichloroethane.

[0086] Optionally, in step (3), the ratio of the compound represented by formula VI to the solvent II is 1 mmol: (100-150) mL.

[0087] Optionally, in step (3), the temperature of reaction III is 90 to 160° C., and the time of reaction III is 3 to 12 hours.

[0088] Optionally, in step (3), the temperature of reaction III is any value of 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, or a range between any two of the above.

[0089] Optionally, in step (3), the time of reaction III is independently selected from any value among 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or a range between any two of the above.

[0090] Optionally, in step (3), the temperature of reaction III is 100-130° C., and the time of reaction III is 4-6 h.

[0091] Optionally, in step (3), the inert atmosphere is selected from nitrogen and / or argon.

[0092] Optionally, in step (4), the catalyst II is tris dibenzylideneacetone dipalladium and tris (o-methylphenyl) phosphine.

[0093] Optionally, in step (4), the molar ratio of the compound represented by formula IX: the compound represented by formula XI: trisdibenzylideneacetone dipalladium: tri(o-methylphenyl)phosphine is: 1:(0.3-0.5):(0.05-0.2):(0.25-0.5).

[0094] Optionally, in step (4), the solvent II is selected from at least one of toluene, chloroform, chlorobenzene and 1,2-dichloroethane.

[0095] Optionally, in step (4), the ratio of the compound represented by formula IX to the solvent II is 1 mmol: (300-350) mL.

[0096] Optionally, in step (4), the temperature of reaction IV is 90 to 160° C., and the time of reaction IV is 3 to 12 hours.

[0097] Optionally, in step (4), the temperature of reaction IV is any value of 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, or a range between any two of the above.

[0098] Optionally, in step (4), the time of reaction IV is independently selected from any value among 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or a range between any two of the above.

[0099] Optionally, in step (4), the temperature of reaction IV is 100-130° C., and the time of reaction IV is 4-6 h;

[0100] Optionally, in step (4), the inert atmosphere is selected from nitrogen and / or argon.

[0101] Optionally, in step (5), the molar ratio of the compound represented by formula XII to the EG3 compound is 1:(1-5).

[0102] Optionally, in step (5), the molar ratio of the compound represented by formula XII to the EG3 compound is independently selected from any value of 1:1, 1:2, 1:3, 1:4, 1:5 or a range between any two of the above values.

[0103] Optionally, in step (5), the catalyst III is selected from at least one of boron trifluoride etherate / acetic anhydride, aluminum trichloride / acetic anhydride, and gallium trichloride / acetic anhydride.

[0104] Optionally, in step (5), the molar ratio of the compound represented by formula XII to the catalyst III is 1:(0.1-1.2);

[0105] Optionally, in step (5), the solvent III is selected from at least one of toluene, chloroform, chloroform, chlorobenzene, and 1,2-dichloroethane.

[0106] Optionally, in step (5), the ratio of the compound represented by formula XII to the solvent III is 1 mmol: (600-700) mL.

[0107] Optionally, in step (5), the temperature of the reaction V is independently selected from any value of 40°C, 45°C, 50°C, 55°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C or a range between any two of the above.

[0108] Optionally, in step (5), the reaction time V is independently selected from any value among 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or a range between any two of the above.

[0109] Optionally, in step (5), the reaction temperature is 40 to 70° C., and the reaction time is 5 to 12 h.

[0110] According to the third aspect of the present application, an electron acceptor material is provided, wherein the electron acceptor material comprises the asymmetric dimerization acceptor material described above.

[0111] According to a fourth aspect of the present application, a semiconductor material is provided, wherein the semiconductor material comprises any one of the electron acceptor materials described.

[0112] According to a fifth aspect of the present application, a photoactive layer is provided, wherein the photoactive layer comprises the semiconductor material.

[0113] According to a sixth aspect of the present application, a film material containing a photoactive layer is provided, wherein the photoactive layer contains the above-mentioned semiconductor material.

[0114] According to a seventh aspect of the present application, an organic solar cell device is provided, wherein the organic solar cell device comprises the semiconductor material or the photoactive layer.

[0115] Optionally, the organic solar cell device comprises a substrate, an anode, an anode modification layer, a photoactive layer, a cathode modification layer and a cathode.

[0116] Optionally, the photoactive layer comprises the asymmetric dimerization acceptor material and an electron donor material.

[0117] Optionally, the mass ratio of the electron donor material to the asymmetric dimerization acceptor material is (0.6-1.5):1.

[0118] Optionally, the mass ratio of the electron donor material to the asymmetric dimerization acceptor material is independently selected from any value of 0.6:1, 0.7:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1 or a range between any two of the above values.

[0119] Optionally, the mass ratio of the electron donor material to the asymmetric dimerization acceptor material is 1:1.

[0120] Optionally, the solar cell device comprises a substrate, an anode, an anode modification layer, a film material containing a photoactive layer, a cathode modification layer and a cathode.

[0121] Optionally, the substrate is glass or polyethylene terephthalate (PET), the anode is indium tin oxide (ITO); the anode modification layer is poly (3,4-ethylenedioxythiophene: polystyrene sulfonate) (PEDOT:PSS); the cathode modification layer is 2,9-bis(3-dimethylaminopropyl)isoquinoline[4',5',6':6,5,10]anthraquino[2,1,9-def]isoquinoline-1,3,8,10(2H,9H)-tetraketone (PDIN); and the cathode is silver (Ag).

[0122] Optionally, the acceptor material is blended with an electron donor material to prepare a photoactive layer, wherein the electron donor material is at least one of PBDB-T, PM6, and PTB7-Th.

[0123] Optionally, the mass ratio of the donor material to the acceptor material in the photoactive layer is (0.6-1.5):1, the solvent used in the photoactive layer is at least one of toluene, xylene, trimethylol, chloroform, chlorobenzene, dichlorobenzene and trichlorobenzene, the concentration of the donor material in the photoactive layer is 1 mg / mL-20 mg / mL, preferably 5 mg / mL-10 mg / mL, and the concentration of the acceptor material can be 1.5 mg / mL-30 mg / mL, preferably 5 mg / mL-15 mg / mL.

[0124] Optionally, the photoactive layer is subjected to annealing treatment at a temperature of 50 to 150° C. for a time of 1 to 30 minutes.

[0125] Optionally, the upper limit of the annealing temperature of the photoactive layer can be independently selected from 150°C, 140°C, 130°C, 120°C, 110°C, 100°C, 90°C, and the lower limit can be independently selected from 50°C, 60°C, 70°C, 80°C, 90°C, 100°C.

[0126] In this application, all conditions involving numerical ranges can be independently selected at any point within the selected range, including the end points of the range.

[0127] In this application, C1~C 30 、C4~C 20 , C3~C 30 、C4~C 20 The numbers of carbon atoms in a group are all referred to, such as C1~C 30 The alkyl group refers to an alkyl group having 1 to 30 carbon atoms.

[0128] In this application, C3~C 30 Branched alkoxy, C3~C 30 Branched fluorinated alkoxy, C3~C 30 Branched alkylthio, C3~C 30 Branched fluorinated alkylthio, C3~C 30 Branched alkyl, C3~C 30 The branched fluorinated alkyl group refers to an alkyl group with at least one or more branches, and the position of the branch can be between C1 and C 29 any location.

[0129] In the present application, "alkyl" refers to a group formed by an alkane compound losing any hydrogen atom, and the alkane compound includes straight-chain alkanes, branched-chain alkanes, and cycloalkanes.

[0130] In the present application, "haloalkyl" refers to a group formed by replacing at least one hydrogen atom on an alkyl group with a halogen atom.

[0131] In the present application, "aryl" is a group formed by losing any hydrogen atom on the aromatic ring in an aromatic compound molecule; the aromatic compound includes a compound containing an aromatic ring and a compound in which at least one hydrogen atom on the aromatic ring is replaced by an alkyl group.

[0132] In the present application, the term "heteroaryl" used herein alone or in combination refers to an arbitrarily substituted heteroaryl group, which contains about 5 to about 20, such as 5 to 12 or 5 to 10 skeleton ring atoms, wherein at least one (such as 1-4, 1-3, 1-2) ring atom is a heteroatom, and the heteroatom is sulfur, but is not limited thereto. The ring of the group does not contain two adjacent O or S atoms. Heteroaryl includes monocyclic heteroaryl (having one ring), bicyclic heteroaryl (having two rings) or polycyclic heteroaryl (having more than two rings). In embodiments where two or more heteroatoms appear in the ring, the two or more heteroatoms may be the same as each other, or some or all of the two or more heteroatoms may be different from each other. Bicyclic heteroaryl or more cyclic heteroaryl may be a monocyclic heteroaryl fused with other independent rings, such as aromatic rings and aromatic heterocycles (collectively referred to as fused ring heteroaryl). Non-limiting examples of monocyclic heteroaryl groups include monocyclic heteroaryl groups of 5 to about 12, 5 to about 10, 5 to about 7 or 6 backbone ring atoms, for example, non-limiting examples thereof include thienyl; fused ring heteroaryl groups include bicyclic thiophene.

[0133] In the present application, "alkoxy" is a group formed by losing a hydrogen atom from a hydroxyl group in an alkyl alcohol molecule.

[0134] In the present application, "alkylthio" refers to a group formed by losing a hydrogen atom from the mercapto group in an alkylthiol molecule.

[0135] In the present application, a "haloalkylthio group" is an alkylthio group in which at least one hydrogen atom is substituted by a halogen atom.

[0136] In the present application, the "halogenated alkylthioaryl group" refers to an alkylthioaryl group in which at least one hydrogen atom on the alkylthio group is substituted by a halogen atom.

[0137] In the present application, "ester group" refers to the ester functional group in the carboxylic acid derivative, with the structural formula -COOR, wherein R is other non-H groups such as alkyl.

[0138] The beneficial effects of this application include:

[0139] (1) The asymmetric dimerization receptor material provided in the present application not only has a monodisperse molecular structure, but also has excellent film-forming properties and good morphological stability and mechanical properties. The prepared photovoltaic device is expected to have both high conversion efficiency and excellent light / thermal stability.

[0140] (2) The asymmetric dimerization receptor material provided in the present application has a planar molecular skeleton, which is conducive to improving the intermolecular π-π stacking, thereby enhancing the efficient transport of carriers between molecules and the conversion efficiency of the device.

[0141] (3) The asymmetric dimerization receptor material provided in the present application can possess the performance advantages of two small molecule receptors and exhibit a higher dielectric constant, low exciton binding energy, a wide absorption spectrum and a highly adjustable energy level. After being blended with an electron donor material, it can achieve a nanoscale phase separation morphology, and the corresponding battery device can simultaneously obtain high short-circuit current, open-circuit voltage and photoelectric conversion efficiency.

[0142] (4) The present application provides a novel synthesis strategy for asymmetric dimerization receptor materials, which can obtain the target dimer material with higher yield and higher purity, and is conducive to large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0143] Figure 1 The asymmetric dimerization receptor material DM-Y prepared in Example 1 of the present application 1 H NMR spectrum.

[0144] Figure 2 The asymmetric dimerization receptor material DM-YF prepared in Example 2 of the present application 1 H NMR spectrum.

[0145] Figure 3 The asymmetric dimerization receptor material DMF-Y prepared in Example 3 of the present application 1 H NMR spectrum.

[0146] Figure 4 The asymmetric dimerization receptor material DMF-YF prepared in Example 4 of the present application 1 H NMR spectrum.

[0147] Figure 5 Ultraviolet-visible absorption (UV-vis) spectra of the asymmetric dimerization receptor material DM-Y prepared in Example 1 of the present application, the asymmetric dimerization receptor material DM-YF prepared in Example 2, the asymmetric dimerization receptor material DMF-Y prepared in Example 3, and the asymmetric dimerization receptor material DMF-YF prepared in Example 4 in the thin film state.

[0148] Figure 6 Ultraviolet-visible absorption (UV-vis) spectra of the asymmetric dimerization receptor material DM-Y prepared in Example 1 of the present application, the asymmetric dimerization receptor material DM-YF prepared in Example 2, the asymmetric dimerization receptor material DMF-Y prepared in Example 3, and the asymmetric dimerization receptor material DMF-YF prepared in Example 4 in solution.

[0149] Figure 7 The cyclic voltammetry curves of the asymmetric dimerization receptor material DM-Y prepared in Example 1 of the present application, the asymmetric dimerization receptor material DM-YF prepared in Example 2, the asymmetric dimerization receptor material DMF-Y prepared in Example 3, and the asymmetric dimerization receptor material DMF-YF prepared in Example 4 in the thin film state.

[0150] Figure 8 The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the asymmetric dimerization acceptor material DM-Y prepared in Example 1 of the present application, the asymmetric dimerization acceptor material DM-YF prepared in Example 2, the asymmetric dimerization acceptor material DMF-Y prepared in Example 3, the asymmetric dimerization acceptor material DMF-YF prepared in Example 4, and the electron donor PM6.

[0151] Fig. 9 This is a current-voltage (JV) curve of the solar cell device prepared with PM6:DM-Y, PM6:DM-YF, PM6:DMF-Y, and PM6:DMF-YF as the active layer in this application. DETAILED DESCRIPTION

[0152] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0153] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0154] Unless otherwise specified, conventional methods were used for testing and instrument settings were those recommended by the manufacturer.

[0155] In the examples of the present application, the prepared asymmetric dimerization receptor material was characterized using the following instruments:

[0156] The obtained materials were tested using a Bruker AVANCE-400 NMR instrument. 1 H NMR spectrum;

[0157] The mass spectrometer was tested using the IonSpec 4.7T Fourier transform mass spectrometer from IonSpec Corporation of the United States;

[0158] Lambda 365 UV-visible spectrophotometer was used to test the UV-visible absorption spectra of the obtained materials in solution and film states;

[0159] The cyclic voltammetry curve of the obtained material in the thin film state was tested using Chenhua 604E electrochemical workstation.

[0160] The method for preparing the asymmetric dimerization receptor material having the structure shown in Formula I in the embodiment of the present application comprises the following steps:

[0161] (1) A material containing compound 1 and a material containing compound 2 are subjected to a Knoevenagel reaction to obtain a material containing compound 3:

[0162]

[0163] (2) A material containing compound 4 and a material containing compound 5 are subjected to a Knoevenagel reaction to obtain a material containing compound 6:

[0164]

[0165] (3) A material containing compound 3 and a material containing compound 7 are subjected to Stille coupling reaction to obtain a material containing compound 8;

[0166]

[0167] (4) A material containing compound 8 and a material containing compound 6 are subjected to Stille coupling reaction to obtain a material containing compound 9;

[0168]

[0169] (5) The material containing compound 9 and the material containing EG3 are reacted by Knoevenagel reaction to obtain the compound of formula I.

[0170]

[0171] Example 1

[0172] The asymmetric dimerization receptor materials shown in Formula I, EG1, EG2 and EG3 are respectively: When the electron-donating unit π is thiophene, the preparation method of the corresponding dimer material is as follows:

[0173]

[0174] (1) BDP-HD and IC-Br are reacted by Knoevenagel reaction to obtain the product BDP-HD-ICBr:

[0175] Synthesis of BDP-HD-ICBr: Compound BDP-HD (100 mg, 0.073 mmol) (synthesized according to the method reported in Natl. Sci. Rev, 2020, 7, 1886-1895) and IC-Br (19 mg, 0.088 mmol) were dissolved in 10 ml of toluene in turn, bubbled for 30 min under a nitrogen atmosphere, and then added with a catalyst 0.2 ml of acetic anhydride and 0.1 ml of boron trifluoride ether, and reacted at room temperature for 30 min. After the reaction, the solvent was removed by a rotary evaporator, and the product was purified by column chromatography (the polarity of the eluent was petroleum ether: dichloromethane = 1:1). The purified product was precipitated in methanol and dried as a black solid with a yield of 60%. The NMR data of BDP-HD-ICBr are: 1 H NMR (400MHz, CDCl3, ppm): δ9.96 (s, 1H), 8.98 (s, 1H), 8.54 (d, J = 8.44Hz, 1H), 8.01 (d, J = 1.94Hz, 1H), 7.93 (s, 1H) ,7.84(dd,J=1.98,8.44Hz,1H),7.73(s,1H),4.75(d,J=7.62Hz,4H),4.01(t,J=7.38Hz,4H),2.11-0.76(m,124H).

[0176]

[0177] (2) Y6HD-CHO and IC-Br are reacted by Knoevenagel reaction to obtain the product Y6HD-ICBr:

[0178] Synthesis of Y6HD-ICBr: Compound Y6HD-CHO (100 mg, 0.080 mmol) (synthesized according to the method reported in Joule 2019, 3, 1140-1151) and IC-Br (17 mg, 0.088 mmol) were dissolved in 10 ml of toluene in turn, bubbled for 30 min under a nitrogen atmosphere, and then added with a catalyst of 0.2 ml of acetic anhydride and 0.1 ml of boron trifluoride ether, and reacted at room temperature for 30 min. After the reaction, the solvent was removed by a rotary evaporator, and the product was purified by column chromatography (the polarity of the eluent was petroleum ether: dichloromethane = 1:1). The purified product was precipitated in methanol and dried to a black solid with a yield of 65%. The NMR data of Y6HD-ICBr are: 1H NMR (400MHz, CDCl3, ppm): δ10.16 (s, 1H), 9.19 (s, 1H), 8.57 (d, J = 8.44Hz, 1H), 8.03 (dd, J = 1.12, 8.48Hz, 1H), 7.86 (dd, J=1.9,8.6Hz,1H),4.73(d,J=7.48Hz,2H),4.65(d,J=7.8Hz,2H),3.22(dd,J=8.36,18.48Hz,4H),2.07-0.67(m,104H).

[0179]

[0180]

[0181] BDP-HD-ICSn: Compound BDP-HD-ICBr (100 mg, 0.062 mmol) and 2,5-bis(trimethyltin)thiophene (253 mg, 0.062 mmol) were dissolved in 20 ml of toluene in sequence, and bubbled for 30 min under nitrogen atmosphere, followed by addition of catalyst Pd2(dba)3 (3.1 mg, 0.0033 mmol) and ligand P(o-tolyl)3 (5.1 mg, 0.0165 mmol), and reacted at 90°C for 2 h. After the reaction, the product was recrystallized and precipitated, and washed with ethanol to obtain a crude product, namely compound BDP-HD-ICSn, which was directly used in the next step.

[0182]

[0183] (4) Compound BDP-HD-ICSn and Y6HD-ICBr were subjected to stille reaction to obtain product DM-Y-CHO: Under nitrogen atmosphere, compound BDP-HD-ICSn (200 mg, 0.060 mmol) was dissolved in 20 ml toluene, and compound Y6HD-ICBr (226 mg, 0.15 mmol) was added, and the mixture was bubbled for 30 min under nitrogen atmosphere, followed by addition of catalyst Pd2(dba)3 (3.1 mg, 0.0030 mmol) and ligand P(o-tolyl)3 (5.1 mg, 0.016 mmol) and reaction at 90°C for 2 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and a dark green solid was separated by gradient elution of a chromatographic column using 200-300 mesh silica gel powder as the stationary phase and petroleum ether and dichloromethane (1:1) as the eluent, with a yield of 55%. The hydrogen NMR data of compound DM-Y-CHO are as follows: 1H NMR (400MHz, CDCl3, ppm): δ10.15(s,1H),9.95(s,1H),9.16(s,1H),8.97(s,1 H),8.73(dd,J=8.40,11.52Hz,2H),8.12(dd,J=1.64,3.56Hz,2H),7.97(m,2H) ,7.91(s,1H),7.72(s,1H),7.63(dd,J=3.92,7.72Hz,2H),4.75(d,J=6.68Hz,6 H),4.66(d,J=5.52Hz,2H),4.01(dd,J=7.0,10.8Hz,4H),3.23-0.64(m,228H).

[0184]

[0185] (5) Compound DM-Y-CHO and IC-2F were reacted by Knoevenagel reaction to obtain product DM-Y: Compound DM-Y-CHO (100 mg, 0.033 mmol) and IC-2F (1.5 mg, 0.066 mmol) were dissolved in 20 mL of toluene at room temperature, and boron trifluoride ether (0.1 mL) and acetic anhydride (0.1 mL) were added in turn. After the reaction, the solvent was removed by rotary evaporator, and the product was purified by column chromatography (the polarity of the eluent was petroleum ether: dichloromethane = 1:1). The purified product was precipitated in methanol and dried to obtain a black solid with a yield of 75%. The hydrogen NMR data of DM-Y is: 1 H NMR (400MHz, CDCl3, ppm): δ9.15 (s, 2H), 8.98 (d, J = 10.20Hz, 2H), 8.74 (t, J = 8.32Hz, 2H), 8.56 (td, J = 7.52, 10.76Hz, 2H), 8.12 (d, J = 5.88Hz, 2H), 7.9 7(t,J=8.40Hz,2H),7.92(s,2H),7.70(td,J=2.74,10.04Hz,2H),7.64(q,J =3.86Hz,2H),4.78(s,8H),4.05(s,4H),3.22(s,4H),2.15-0.65(m,228H).

[0186] Example 2

[0187] The asymmetric dimerization receptor materials shown in Formula I, EG1, EG2 and EG3 are respectively: When the electron-donating unit π is thiophene, the preparation method of the corresponding dimer material is as follows:

[0188]

[0189] (1) The preparation of BDP-HD-ICBr is the same as in Example 1.

[0190] (2) Y6HD-CHO and IC-2FBr are reacted by Knoevenagel reaction to obtain the product Y6HD-IC2FBr:

[0191] The synthesis steps of Y6HD-IC2FBr refer to Y6HD-ICBr. Compound Y6HD-IC2FBr is a dark green solid with a yield of 62%. The NMR data of Y6HD-IC2FBr are: 1 H NMR (400MHz, CDCl3, ppm): δ10.16 (s, 1H), 9.18 (s, 1H), 8.35 (d, J = 8.12Hz, 1H), 4.6 9(dd,J=7.52,28.52Hz,4H),3.22(dd,J=9.44,16.96Hz,4H),2.07-0.68(m,104H).

[0192]

[0193] (3) The preparation of BDP-HD-ICSn is the same as that in Example 1.

[0194] (4) Compound BDP-HD-ICSn and compound Y6HD-IC2FBr were reacted by stille reaction to obtain product DM-YF-CHO: the specific synthesis route refers to the above compound DM-Y-CHO. DM-YF-CHO is a dark green solid with a yield of 52%. The hydrogen NMR data of compound DM-YF-CHO are: 1 H NMR (400MHz, CDCl3, ppm): δ10.16(s,1H),9.96(s,1H),9.14(s,1H),8.98(s,1H),8.73(d,J =8.34Hz,1H),8.43(d,J=10.84Hz,1H),8.14(s,1H),8.00(dd,J=1.28,8.28Hz,1H),7.95(s, 1H),7.91(d,J=3.80Hz,1H),7.73(s,1H),7.68(d,J=3.80Hz,1H),4.76(d,J=4.60Hz,4H),4 .67(d,J=7.28Hz,4H),4.03(t,J=8.38Hz,4H),3.21(t,J=8.02Hz,4H),2.12-1.97(m,228H).

[0195]

[0196] (5) Compound DM-YF-CHO and IC-2F were reacted by Knoevenagel reaction to obtain product DM-YF: The specific synthesis steps and parameters of DM-YF refer to the above compound DM-Y, wherein the amount of M-YF-CHO was 0.033 mmol. The obtained DM-YF was a black solid with a yield of 77%. The hydrogen NMR data of DM-YF is 1 H NMR (400MHz, CDCl3, ppm): δ9.16(s,1H),9.13(s,1H),8.98(s,1H),8.96(s,1 H),8.73(d,J=8.28Hz,1H),8.55(m,2H),8.43(d,J=11.00Hz,1H),8.13(s,1H) ,8.01(dd,J=1.90,8.22Hz,1H),7.94(s,1H),7.90(d,J=3.32Hz,2H),7.70(m ,3H),4.78(s,8H),4.05(d,J=6.64Hz,4H),3.22(m,4H),2.15-0.71(m,228H).

[0197] Example 3

[0198] The asymmetric dimerization receptor materials shown in Formula I, EG1, EG2 and EG3 are respectively: When the electron-donating unit π is thiophene, the preparation method of the corresponding dimer material is as follows:

[0199]

[0200] (1) BDP-HD and IC-2FBr are reacted by Knoevenagel reaction to obtain the product BDP-HD-IC2FBr:

[0201] The specific synthesis steps of BDP-HD-IC2FBr refer to BDP-HD-ICBr. The target compound BDP-HD-IC2FBr is a dark blue oil with a yield of 58%. The NMR data of BDP-HD-IC2FBr are: 1 H NMR (400MHz, CDCl3, ppm): δ9.96 (s, 1H), 8.97 (s, 1H), 8.30 (d, J = 8.04Hz, 1H), 7.88 (s, 1H), 7.73(s,1H),4.75(d,J=7.36Hz,4H),4.01(dd,J=7.12,11.04Hz,4H),2.12-0.72(m,124H).

[0202]

[0203] (2) The preparation of Y6HD-ICBr is the same as that in Example 1.

[0204] (3) Compound BDP-HD-IC2FBr and 2,5-bis(trimethyltin)thiophene were reacted by stille reaction to obtain product BDP-HD-IC2FSn: the specific synthesis of compound BDP-HD-IC2FSn was referenced to compound BDP-HD-ICSn. After the reaction was completed, the product was recrystallized and washed with ethanol to obtain a crude product, namely compound BDP-HD-IC2FSn, which was directly used in the next reaction.

[0205]

[0206] (4) Compound Y6HD-ICBr and compound BDP-HD-IC2FSn were reacted by stille reaction to obtain product DMF-Y-CHO: the specific synthesis route refers to the above compound DM-Y-CHO. DMF-Y-CHO is a dark green solid with a yield of 53%. The hydrogen spectrum NMR data of compound DMF-Y-CHO are: 1 H NMR (400MHz, CDCl3, ppm): δ10.16(s,1H),9.96(s,1H),9.18(s,1H),8.97(s,1H ),8.76(d,J=8.4Hz,1H),8.40(d,J=10.46Hz,1H),8.16(s,1H),8.03(d,J=9.48 Hz,1H),7.91(s,2H),7.73(s,1H),7.67(d,J=3.16Hz,1H),4.76(d,J=6.08Hz,5 H),4.68(d,J=8.2Hz,3H),4.02(dd,J=6.44,12.48Hz,4H),3.28-0.70(m,228H).

[0207]

[0208] (5) Compound DMF-Y-CHO and IC-2F were reacted by Knoevenagel reaction to obtain product DMF-Y: The specific synthesis steps and parameters of DMF-Y refer to the above compound DM-Y, wherein the amount of DMF-Y-CHO was 0.033 mmol. The obtained DMF-Y was a black solid with a yield of 72%. The hydrogen NMR data of DM-YF is 1H NMR (400MHz, CDCl3, ppm): δ9.15 (s, 2H), 8.96 (s, 2H), 8.73 (d, J = 8.26Hz, 1H) ,8.57(s,J=12.00Hz,1H),8.52(s,J=10.88Hz,1H),8.40(d,J=11.08Hz,1H),8 .12(s,1H),8.00(d,J=8.32Hz,1H),7.91(t,J=3.12Hz,3H),7.69(m,3H),4.78 (m,8H),4.05(d,J=7.24Hz,4H),3.21(d,J=8.60Hz,4H),2.15-0.67(m,228H).

[0209] Example 4

[0210] The asymmetric dimerization receptor materials shown in Formula I, EG1, EG2 and EG3 are respectively: When the electron-donating unit π is thiophene, the preparation method of the corresponding dimer material is as follows:

[0211]

[0212] (1) The preparation of Y6HD-IC2FBr is the same as that in Example 2.

[0213] (2) The preparation of BDP-HD-IC2FBr is the same as that in Example 3.

[0214] (3) The preparation of BDP-HD-IC2FSn is the same as that in Example 3.

[0215] (1) The above compound Y6HD-IC2FBr and the compound BDP-HD-IC2FSn are reacted by stille reaction to obtain the product DMF-YF-CHO: the specific synthesis route refers to the above compound DM-Y-CHO. DMF-YF-CHO is a dark green solid with a yield of 51%. The hydrogen spectrum nuclear magnetic resonance data of the compound DMF-YF-CHO are: 1 H NMR (400MHz, CDCl3, ppm): δ10.16(s,1H),9.96(s,1H),9.19(s,1H),8.99(s,1H),8.43(t,J=11.68,2 H),7.94(s,2H),7.73(s,1H),4.76(d,J=7.28Hz,3H),4.66(d,J=7.16Hz,4H),4.02(dd,J=7.28,9.8Hz 4H),3.22(m,4H),2.17-0.69(m,J=7.6Hz,228H).

[0216]

[0217] (2) Compound DMF-YF-CHO and IC-2F were reacted by Knoevenagel reaction to obtain product DMF-YF: The specific synthesis steps and parameters of DMF-YF refer to the above compound DM-Y, wherein the amount of DMF-YF-CHO was 0.033 mmol. The obtained DMF-YF was a black solid with a yield of 70%. The hydrogen spectrum NMR data of DMF-YF is 1 HNMR (400MHz, CDCl3, ppm): δ9.18 (s, 2H), 8.99 (s, 1H), 8.96 (s, 1H), 8.56 (m, 3H), 8.44 (t, J = 10.24Hz, 2H), 7. 95(s,2H),7.92(s,1H),7.70(t,J=7.38Hz,2H),4.76(s,8H),4.03(s,4H),3.24(s,4H),2.13-0.69(m,228H).

[0218] Example 5

[0219] A solar cell device was prepared using the dimerized receptor material DM-Y prepared in Example 1 and tested.

[0220] The solar cell device adopts an upright device structure:

[0221] Glass substrate / ITO (indium tin oxide) / PEDOT (polyethylene dioxythiophene): PSS (sodium polystyrene sulfonate) / active layer / PDIN (2,9-bis(3-dimethylaminopropyl)isoquinoline[4′,5′,6′:6,5,10]anthraquino[2,1,9-def]isoquinoline-1,3,8,10(2H,9H)-tetraone) / silver. Among them, the ITO layer is attached to the glass substrate, and the ITO and glass substrate are collectively referred to as ITO glass. The ITO glass is washed with detergent, water, acetone and isopropanol in sequence under ultrasound for thirty minutes each. Then it is dried in an oven at 90°C overnight. After the ITO glass is treated with ultraviolet ozone for 15 minutes, PEDOT:PSS is spin-coated on the ITO layer, and it is placed in a 140°C oven for heating for 15 minutes, and then quickly transferred to a glove box for standby use. The polymer donor PM6 (purchased from Shuo Lun Organic Photoelectric Technology (Beijing) Co., Ltd.) and the dimerized receptor material DM-Y obtained in Example 1 were dissolved in chloroform at a weight ratio of 1:1, and 0.5% by volume of 1-chloronaphthalene was added as an additive. The total concentration of the solution was 15 mg / mL. The solution was stirred at 50°C for 4 hours, and then the solution was spin-coated on the PEDOT:PSS film as an active layer with a thickness of about 100 nm. In order to improve the electron injection efficiency and block holes at the same time, a methanol solution of PDIN (1.5 mg / mL containing 0.2% acetic acid by mass) was spin-coated on the active layer. Finally, the negative electrode of the battery was placed in a vacuum of about 5×10 -5 The device was completed by thermal evaporation of 100nm silver electrode under Pa conditions, and the area of ​​the device was 4.15mm 2 .

[0222] Commercial PM6 was purchased from ShuoLun Organic Photoelectric Technology (Beijing) Co., Ltd. n It is about 41 kg / mol, PDI is about 2.0, and its structure is as follows:

[0223]

[0224] Example 6

[0225] Same as Example 5, the only difference is that the active layer is PM6:DM-YF.

[0226] Example 7

[0227] Same as Example 6, the only difference is that the active layer is PM6:DMF-Y.

[0228] Example 8

[0229] Same as Example 7, the only difference is that the active layer is PM6:DMF-YF.

[0230] Test Example 1

[0231] The performance tests were performed on the devices obtained in Examples 5 to 8:

[0232] The device was tested using an Oriel sol3A (Newport) solar simulator simulating AM 1.5G (100mW / cm 2 ) and measured using a Keithley 2400 digital source meter tester.

[0233] The parameters of the solar cell devices obtained in Examples 5 to 8 are summarized in Table 1, including the open circuit voltage (V oc ), short circuit current (J sc ), fill factor (FF) and photoelectric conversion efficiency (PCE), and the corresponding current-voltage curves are shown in Fig. 9 .

[0234] Table 1 Parameters of solar cell devices prepared based on the asymmetric dimerization receptor material

[0235]

[0236] From Table 1 and Fig. 9 As can be seen from the figure, organic solar cells based on asymmetric dimerization acceptor materials have achieved high PCE. With the increase of fluorine atoms on the end groups, the V of devices based on DM-Y, DM-YF, DMF-Y and DMF-YF oc They are 0.936V, 0.906V, 0.908V, and 0.88V respectively. sc and FF both show a trend of increasing first and then decreasing. Finally, the DM-Y-based device achieves a PCE of up to 18.68%, which is higher than the device efficiencies of DM-YF (18.18%), DMF-Y (17.33%), and DMF-YF (16.50%).

[0237] Test Example 2

[0238] The acceptor material provided in Example 1 was tested for its molecular light absorption characteristics and electrochemical properties.

[0239] Test methods include:

[0240] The light absorption properties of the dimeric non-fullerene acceptor materials DM-Y, DM-YF, DMF-Y and DMF-YF were tested using a UV / visible / near-infrared spectrophotometer from PerkinElmer (Lambda365).

[0241] The electrochemical properties of the dimeric receptor materials DM-Y, DM-YF, DMF-Y and DMF-YF were tested using Shanghai Chenhua Instrument Co., Ltd. (CHI 604E).

[0242] The UV-visible absorption spectrum and cyclic voltammetry curve in Test Example 2 are shown in Figures 5 to 7 .

[0243] Figure 5 The absorption spectra of DM-Y, DM-YF, DMF-Y and DMF-YF in thin film state. It can be seen that the absorption of the four materials can extend to the near-infrared region, so they can make full use of sunlight in the near-infrared region.

[0244] from Figure 6 It can be seen that the absorption spectra of DM-Y, DM-YF, DMF-Y and DMF-YF in solution show similar shapes, where the absorption in the range of 650-800 nanometers is caused by the π-π* transition within the molecule. As the number of fluorine atoms on the end group increases, the absorption of the corresponding asymmetric dimerization receptor material gradually red-shifts. Although both DM-YF and DMF-Y contain 6 fluorine atoms, DM-YF and DMF-Y show red-shifted absorption spectra, which is related to their more effective intramolecular charge transfer effect.

[0245] Figure 7 The cyclic voltammetry curves of DM-Y, DM-YF, DMF-Y and DMF-YF in the thin film state are shown in Figure 2. According to their initial redox positions, the highest occupied molecular orbital energy levels of the four can be calculated to be -5.70 eV, -5.72 eV, -5.72 eV and -5.75 eV, respectively, while the lowest unoccupied molecular orbital energy levels are -4.05 eV, -3.98 eV, -4.15 eV and -4.12 eV, respectively. For details, see Figure 8 shown.

[0246] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An asymmetric dimerization receptor material, characterized in that: The asymmetric dimerization receptor material has the structure described in Formula I; Wherein, R1, R2, R3, R4 are independently selected from C1 to C 30 Alkyl I, C1~C 30 The halogenated alkyl I, C4~C 20 Aryl I, C4~C 20 The substituted aryl group I has one of the groups shown in formula I-1; R'—M—*Formula I-1; In formula I-1, R' is selected from C1 to C 30 Alkyl II, C1~C 30 One of the haloalkyl II; M is selected from O or S; The substituent of the substituted aryl group I is selected from one of alkyl, haloalkyl, alkoxy, haloalkoxy, halogen, alkylthio, and haloalkylthio; X1, X2 are independently selected from O, S, Se or Te; Ar1, Ar2 are independently selected from C4~C 20 wherein the aryl group contains at least one thiophene ring which forms a condensed ring with the pyrrole ring in formula I; EG1, EG2, and EG3 are independently selected from one of the groups having the structure shown in Formula II, wherein the dotted line in Formula II is the double bond connection position; In formula II, Ar3 is selected from C4~C 40 Aryl II, C4~C 40 Substituted aromatic II, C3~C 40 Heteroaryl, C3~C 40 One of the substituted heteroaryl groups; The substituents of the substituted aryl II and the substituted heteroaryl are independently selected from any one of halogen, cyano, haloalkyl, alkyl, alkoxy, alkylthio, ester and carbonyl; The π group in formula I is selected from thiophene, One of the groups of the structure shown.

2. The asymmetric dimerization receptor material according to claim 1, characterized in that: The EG1 and EG2 are independently selected from one of the structures shown in formula II-1, formula II-2, formula II-3, formula II-4, formula II-5, and formula II-6; In Formula II-1 to Formula II-6, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 is independently selected from one of a hydrogen atom, a halogen, a cyano group, a C1-C30 alkyl group III, a C1-C30 alkoxy group I, a C1-C30 alkylthio group I, a C1-C30 ester group I, and a carbonyl group I; Preferably, EG1 and EG2 are independently selected from at least one of 5-bromocyanoindanone, 4-fluoro-5-bromocyanoindanone, 4,6-difluoro-5-bromocyanoindanone, 4-chloro-5-bromocyanoindanone and 4,6-dichloro-5-bromocyanoindanone; Preferably, the EG3 is selected from one of the structures shown in formula II-7, formula II-8, formula II-9, formula II-10, formula II-11, formula II-12, formula II-13, formula II-14, formula II-15, formula II-16, formula II-17, formula II-18, and formula II-19; In Formula II-7 to Formula II-19, the R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 Independently selected from one of hydrogen atom, halogen, cyano, C1-C30 alkyl IV, C1-C30 alkoxy II, C1-C30 alkylthio II, C1-C30 ester II, and carbonyl II; Preferably, the EG3 is selected from at least one of 5,6-difluoro-3-(dicyanomethylene)indone, 3-(dicyanomethylene)indone, 5,6-dichloro-3-(dicyanomethylene)indone, 6-fluoro-3-(dicyanomethylene)indone and 6-chloro-3-(dicyanomethylene)indone.

3. The asymmetric dimerization receptor material according to claim 1, characterized in that: The π group in formula I is selected from one of the structures shown in formula III-1, formula III-2, formula III-3, formula III-4, formula III-5, formula III-6, formula III-7, and formula III-8; Wherein, X3 is selected from O, S or Se; R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 29 , R 30 Any one independently selected from halogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and ester; R 28 One selected from C1 to C30 alkyl groups; Preferably, the π group in formula I is selected from one of 2,5-bis(trimethyltin)thiophene, 2,5-bis(trimethyltin)thiophene[3,2-b]thiophene, 5,5′-bis(trimethyltin)-2,2′-bithiophene, (3,3′-difluoro-[2,2′-bithiophene]-5,5′-diyl)bistrimethyltin, and 2,6-bis(trimethyltin)benzo[1,2-b:4,5-b′]bithiophene.

4. The method for preparing the asymmetric dimerization receptor material according to any one of claims 1 to 3, characterized in that: The steps include: (1) reacting a mixture I containing a compound represented by formula IV, a compound represented by formula V, a catalyst I, and a solvent I to obtain a compound represented by formula VI; (2) reacting a mixture II containing the compound represented by formula VII, the compound represented by formula VIII, a catalyst I, and a solvent I to obtain a compound represented by formula IX; (3) reacting a mixture III containing the compound represented by formula VI, the compound represented by formula X, a catalyst II, and a solvent II in an inert atmosphere to obtain a compound represented by formula XI; (4) reacting a mixture IV containing the compound represented by formula IX, the compound represented by formula XI, a catalyst II, and a solvent II in an inert atmosphere to obtain a compound represented by formula XII; (5) reacting a mixture V containing the compound represented by formula XII, the EG3 compound, the solvent III, and the catalyst III to obtain an asymmetric dimerization receptor material having a structure represented by formula I; 5. The preparation method according to claim 4, characterized in that: In step (1), the molar ratio of the compound represented by formula IV to the compound represented by formula V is 1:(0.8-1.3); Preferably, in step (1), the catalyst I is acetic anhydride and boron trifluoride etherate; Preferably, in step (1), the amount of catalyst I added is 0.5% to 5% of the molar amount of the compound represented by formula IV; Preferably, in step (1), the molar ratio of the acetic anhydride to the boron trifluoride etherate is 1:(0.1-1.2); Preferably, in step (1), the solvent I is selected from at least one of toluene, chloroform, chlorobenzene and 1,2-dichloroethane; Preferably, in step (1), the ratio of the compound represented by formula IV to the solvent I is 1 mmol: (100-150) mL; Preferably, in step (1), the temperature of reaction I is 0 to 50° C., and the time of reaction I is 10 to 60 min; Preferably, in step (2), the molar ratio of the compound represented by formula VII to the compound represented by formula VIII is 1:(0.8-1.2); Preferably, in step (2), the catalyst I is acetic anhydride and boron trifluoride etherate; Preferably, in step (2), the amount of catalyst I added is 0.5% to 5% of the molar amount of the compound represented by formula VII; Preferably, in step (2), the molar ratio of the acetic anhydride to the boron trifluoride etherate is 1:(0.1-1.2); Preferably, in step (2), the solvent I is selected from at least one of toluene, chloroform, chlorobenzene, and 1,2-dichloroethane; Preferably, in step (2), the ratio of the compound represented by formula VII to the solvent I is 1 mmol: (100-150) mL; Preferably, in step (2), the temperature of reaction II is 0 to 50° C., and the time of reaction II is 10 to 60 min; Preferably, in step (3), the catalyst II is tris dibenzylideneacetone dipalladium and tris (o-methylphenyl) phosphine; Preferably, in step (3), the molar ratio of the compound represented by formula VI: the compound represented by formula X: tris dibenzylideneacetone dipalladium: tris (o-methylphenyl) phosphine is 1: (0.8-1.5): (0.05-0.2): (0.25-0.5); Preferably, in step (3), the solvent II is selected from at least one of toluene, chloroform, chlorobenzene, and 1,2-dichloroethane; Preferably, in step (3), the ratio of the compound represented by formula VI to the solvent II is 1 mmol: (300-350) mL; Preferably, in step (3), the temperature of reaction III is 90 to 160° C., and the time of reaction III is 3 to 12 h; Preferably, in step (3), the inert atmosphere is selected from nitrogen and / or argon; Preferably, in step (4), the catalyst II is tris dibenzylideneacetone dipalladium and tris (o-methylphenyl) phosphine; Preferably, in step (4), the molar ratio of the compound represented by formula IX: the compound represented by formula XI: trisdibenzylideneacetone dipalladium: tris(o-methylphenyl)phosphine is: 1: (0.3-0.5): (0.05-0.2): (0.25-0.5); Preferably, in step (4), the solvent II is selected from at least one of toluene, chloroform, chlorobenzene, and 1,2-dichloroethane; Preferably, in step (4), the ratio of the compound represented by formula IX to the solvent II is 1 mmol: (300-350) mL; Preferably, in step (4), the temperature of reaction IV is 90 to 160° C., and the time of reaction IV is 3 to 12 h; Preferably, in step (4), the inert atmosphere is selected from nitrogen and / or argon; Preferably, in step (5), the molar ratio of the compound represented by formula XII to the EG3 compound is 1:(1-5); Preferably, in step (5), the catalyst III is selected from at least one of boron trifluoride etherate / acetic anhydride, aluminum trichloride / acetic anhydride, and gallium trichloride / acetic anhydride. ; Preferably, in step (5), the molar ratio of the compound represented by formula XII to the catalyst III is 1:(0.1-1.2); Preferably, in step (5), the solvent III is selected from at least one of toluene, chloroform, chloroform, chlorobenzene, and 1,2-dichloroethane; Preferably, in step (5), the ratio of the compound represented by formula XII to the solvent III is 1 mmol: (600-700) mL; Preferably, in step (5), the temperature of reaction V is 40 to 70° C., and the time of reaction V is 5 to 12 h.

6. An electron acceptor material, characterized in that The electron acceptor material comprises the asymmetric dimerization acceptor material according to any one of claims 1 to 4.

7. A semiconductor material, characterized in that: The semiconductor material comprises the electron acceptor material according to claim 6.

8. A photoactive layer, characterized in that The photoactive layer comprises the semiconductor material of claim 7.

9. A film material containing a photoactive layer, characterized in that: The photoactive layer comprises the semiconductor material of claim 7.

10. An organic solar cell device, characterized in that: The organic solar cell device comprises the semiconductor material of claim 7 or the photoactive layer of claim 8; Preferably, the organic solar cell device comprises a substrate, an anode, an anode modification layer, a photoactive layer, a cathode modification layer and a cathode; Preferably, the photoactive layer comprises the asymmetric dimerization acceptor material and an electron donor material; Preferably, the mass ratio of the electron donor material to the asymmetric dimerization acceptor material is (0.6-1.5):1; preferably, the mass ratio of the electron donor material to the asymmetric dimerization acceptor material is 1:1.

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