Compounds, their stereoisomers or optical isomers and preparation methods, donor materials, solar cells, electrical devices and applications

Abstract

This invention belongs to the field of solar cells, specifically relating to compounds represented by Formula I, their stereoisomers, or optical isomers. This invention also relates to methods for preparing the above-mentioned compounds, their stereoisomers, or optical isomers, solar cell donor materials, solar cells, electrical devices, and applications.

Description

Technical Field

[0001] This invention belongs to the field of solar cells, specifically relating to compounds, their stereoisomers or optical isomers, methods for preparing the compounds, their stereoisomers or optical isomers, solar cell donor materials, solar cells, electrical devices, and applications. Background Technology

[0002] Organic solar cells have attracted widespread attention due to their significant advantages such as flexibility, light weight, semi-transparency, and ability to be processed and produced on a large scale, indicating that organic solar cells have broad development prospects.

[0003] Compared to organic solar cells fabricated using solution methods, organic solar cells fabricated using vacuum evaporation exhibit higher stability. Furthermore, vacuum evaporation technology has been successfully applied in the commercial field of organic light-emitting diodes (OLEDs), demonstrating greater potential for practical commercial applications. However, the photoelectric conversion efficiency of vacuum-evaporated organic solar cells is relatively low. This is partly due to the limited molecular weight of the donor and acceptor molecules, resulting in weaker optical properties and lower short-circuit current. Additionally, research on donor molecules for vacuum-evaporated organic solar cells is relatively scarce, with a limited number of studies available.

[0004] Therefore, it is urgent to design and synthesize donor molecules with high stability and strong visible and near-infrared absorption, and to improve the photoelectric conversion efficiency of vacuum-deposited organic solar cells. Summary of the Invention

[0005] One objective of this invention is to provide a compound, its stereoisomers, or optical isomers, which possess good stability and excellent optical properties, thereby improving the photoelectric conversion efficiency of vacuum-deposited organic solar cells. Another objective of this invention is to provide a method for preparing the aforementioned compound, its stereoisomers, or optical isomers. Yet another objective of this invention is to provide solar cell donor materials, solar cells, electrical devices, and their applications.

[0006] To achieve the above objectives, the first aspect of the present invention provides a compound of Formula I, its stereoisomers or optical isomers,

[0007]

[0008] in,

[0009] D is selected from Among them, R1, R2, R5, and R6 are each independently selected from C. 1-6 Alkyl group; R3 is selected from 5-10-membered heteroaryl groups, or R3 forms a 5-10-membered heteroaryl group with the carbon atom attached to the benzene ring and the adjacent carbon atom, or R3 is absent; R4 is C 1-6Alkylsilyl groups, or R4, form 5-10 membered aromatic rings with carbon atoms attached to and adjacent carbon atoms on a five-membered ring; Y is selected from S, N, Se, and O; m is 0 or 1;

[0010] π is Wherein, the G ring is selected from 5-10 aryl and 5-10 heteroaryl groups; X is selected from O, S, Se, CH, or X includes a carbon atom and forms a ring with the adjacent carbon atom on the ring. R7 and R8 are each independently selected from H, halogen atoms, and C. 1-6 Alkyl; E is selected from S, O, Se, and N; n is 0 or 1;

[0011] A is selected from Among them, R9 and R 10 Each is independently selected from O and dicyanoC. 1-6 Alkylene (e.g., dicyanoC) 1-4 Alkylene, dicyano C 1-2 Alkylene, dicyano C 2-6 Alkylene, dicyano C 2-4 Alkylene);

[0012] Furthermore, the compound is not one of the following:

[0013]

[0014] In any embodiment of the first aspect of the present invention, D is selected from...

[0015] Among them, R1, R2, R5, and R6 are each independently selected from C. 1-6 Alkyl group; R3 is selected from 5-6 membered heteroaryl groups containing O, S, or Se atoms, or R3 forms a 5-6 membered heteroaryl group containing O, S, or Se atoms with the carbon atom attached to the benzene ring and the adjacent carbon atom, or R3 is absent; R4 is a tricarbonyl group. 1-6 Alkylsilyl, or R4, forms a 5-6 membered aromatic ring with a carbon atom attached to the five-membered ring and a carbon atom in the adjacent position; Y is selected from S and N; m is 0 or 1.

[0016] In any embodiment of the first aspect of the present invention, D is selected from...

[0017] R1, R2, R5, and R6 are each independently selected from methyl and isobutyl groups; R3 is selected from... Alternatively, R3 may form a furanyl or thiophene group with the carbon atom attached to the benzene ring and the adjacent carbon atom, or R3 may not exist; R4 may be a triisopropylsilyl group, or R4 may form a benzene ring with the carbon atom attached to the five-membered ring and the adjacent carbon atom; Y may be selected from S and N; m may be 0 or 1.

[0018] In any embodiment of the first aspect of the present invention, D is selected from...

[0019] R1, R2, R5, and R6 are each independently selected from methyl and isobutyl groups; R3 is selected from... Alternatively, R3 may form a ring with the carbon atom attached to the benzene ring and the adjacent carbon atom. Alternatively, R3 may not exist; R4 may be triisopropylsilyl, or R4 may form a benzene ring with the carbon atom attached to the five-membered ring and the adjacent carbon atom; Y may be selected from S and N; m may be 0 or 1.

[0020] In any embodiment of the first aspect of the present invention, D is selected from...

[0021] In any embodiment of the first aspect of the present invention, D is a donor group.

[0022] In any embodiment of the first aspect of the present invention, π is

[0023] Wherein, the G ring is selected from 5-6 aryl and 5-6 heteroaryl groups; X is selected from O, S, Se, CH, or X includes a carbon atom and forms a ring with the adjacent carbon atom on the ring. R7 and R8 are each independently selected from H, halogens, and C. 1-6 Alkyl; E is selected from S, O, Se and N; n is 0 or 1.

[0024] In any embodiment of the first aspect of the present invention, D is When π is not

[0025] In any embodiment of the first aspect of the present invention, π is

[0026] Wherein, ring G is selected from phenyl and 5-membered heteroaryl; X is selected from O, S, Se, CH, or X includes a carbon atom and forms a ring with the carbon atom adjacent to it. R7 and R8 are each independently selected from H, halogen, methyl, n-butyl and isobutyl; E is selected from S and N; n is 0 or 1.

[0027] In any embodiment of the first aspect of the present invention, π is selected from any of the following groups:

[0028] X1 is selected from O, S and Se; X2 and X3 are each independently selected from H, halogen, methyl, n-butyl and isobutyl.

[0029] In any embodiment of the first aspect of the present invention, π is selected from any of the following groups:

[0030] X1 is selected from O, S and Se; X2 is selected from H, F and Cl; X3 is selected from methyl, n-butyl and isobutyl.

[0031] In any embodiment of the first aspect of the present invention, A is selected from... Among them, R9 and R 10 Each is independently selected from O and dicyanomethylene.

[0032] In any embodiment of the first aspect of the present invention, A is selected from any of the following groups:

[0033]

[0034] In any embodiment of the first aspect of the present invention, A is selected from... Among them, R9 and R 10 One is O, and the other is dicyanoC. 1-6 Alkylene.

[0035] In any embodiment of the first aspect of the present invention, A is selected from any of the following groups:

[0036]

[0037] In any embodiment of the first aspect of the present invention, A is a receptor group.

[0038] In any embodiment of the first aspect of the present invention, the compound is selected from:

[0039]

[0040] The "dashed line" in the above groups indicates a free end on the group that can be bonded to the parent nucleus or other groups.

[0041] The second aspect of this invention provides a method for preparing the compound of the first aspect of this invention, its stereoisomers, or its optical isomers, which may be method one, method two, or method three; wherein,

[0042] Method 1 includes the following steps:

[0043] The compound represented by formula M and the compound represented by formula B undergo a coupling reaction in a solvent to give the compound represented by formula C, as shown in the following reaction formula:

[0044]

[0045] The compound represented by formula C undergoes a condensation reaction with a compound containing the A group in a solvent to give the compound represented by formula I, as shown in the following reaction formula:

[0046]

[0047] The second method includes the following steps:

[0048] The compound represented by formula N undergoes a lithiation reaction and a lithium halide exchange reaction with tributyltin chloride in a solvent to give the compound represented by formula F, as shown in the following reaction formula:

[0049]

[0050] The compound represented by formula F undergoes a coupling reaction with the compound represented by formula H in a solvent to give the compound represented by formula I, as shown in the following reaction formula:

[0051]

[0052] Method 3 includes the following steps:

[0053] The compound represented by formula F undergoes a coupling reaction with the compound represented by formula B in a solvent to give the compound represented by formula C, as shown in the following reaction formula:

[0054]

[0055] The compound represented by formula C undergoes a condensation reaction with a compound containing the A group in a solvent to give the compound represented by formula I, as shown in the following reaction formula:

[0056]

[0057] The D, π, and A groups are defined as described in the first aspect of this invention.

[0058] In any embodiment of the second aspect of the present invention, one or more of the following are characterized:

[0059] 1) In Method 1, the coupling reaction uses Pd(PPh3)4 catalyst;

[0060] 2) In Method 1, the molar ratio of the compound represented by Formula M to the compound represented by Formula B is 1:2-1:4;

[0061] 3) In Method 1, the solvent used in the coupling reaction is selected from one or more of tetrahydrofuran, water, and toluene;

[0062] 4) In Method 1, the coupling reaction temperature is 90-130℃;

[0063] 5) In Method 1, the coupling reaction time is 16-30 hours;

[0064] 6) In Method 1, the solvent used in the condensation reaction is acetic acid;

[0065] 7) In Method 1, the temperature of the condensation reaction is 10-30℃;

[0066] 8) In Method 1, the condensation reaction time is 10-30 hours;

[0067] 9) In Method 2, the solvent used for the lithiation reaction and the lithium halide exchange reaction is tetrahydrofuran;

[0068] 10) In Method 2, the temperature for the lithiation reaction and the lithium halide exchange reaction is -60 to 80°C;

[0069] 11) In Method 2, the time for the lithiation reaction and the lithium halide exchange reaction is 10-30 h;

[0070] 12) In Method 2, the coupling reaction uses Pd(PPh3)2Cl2 catalyst;

[0071] 13) In Method 2, the molar ratio of the compound represented by Formula F to the compound represented by Formula H is 1:3-1:5;

[0072] 14) In Method 2, the solvent used in the coupling reaction is selected from one or more of tetrahydrofuran, dioxane, and toluene, or a mixture thereof;

[0073] 15) In Method 2, the coupling reaction temperature is 100-150℃;

[0074] 16) In Method 2, the coupling reaction time is 16-30 hours;

[0075] 17) In Method 3, the coupling reaction uses Pd(PPh3)2Cl2 catalyst;

[0076] 18) In Method 3, the molar ratio of the compound shown in Formula F to the compound shown in Formula B is 1:3-1:5;

[0077] 19) In Method 3, the solvent used in the coupling reaction is selected from one or more of tetrahydrofuran, dioxane, and toluene, or a mixture thereof;

[0078] 20) In Method 3, the coupling reaction temperature is 100-150℃;

[0079] 21) In Method 3, the coupling reaction time is 16-30 h;

[0080] 22) In Method 3, the solvent used in the condensation reaction is chloroform;

[0081] 23) In Method 3, the temperature of the condensation reaction is 15-35℃;

[0082] 24) In Method 3, the condensation reaction time is 5-10 hours.

[0083] A third aspect of the present invention provides a solar cell donor material, comprising the compound of the first aspect of the present invention, its stereoisomer or optical isomer, or the compound prepared by the method of the second aspect of the present invention, its stereoisomer or optical isomer;

[0084] Optionally, the solar cell donor material is an organic solar cell donor material, and more preferably a vacuum-deposited organic solar cell donor material.

[0085] A fourth aspect of the present invention provides a solar cell comprising a compound of the first aspect of the present invention, a stereoisomer thereof or an optical isomer thereof, or a compound prepared by the method of the second aspect of the present invention, a stereoisomer thereof or an optical isomer thereof, or a solar cell donor material of the third aspect of the present invention.

[0086] In any embodiment of the fourth aspect of the present invention, it is characterized by one or more of the following:

[0087] (1) The solar cell is an organic solar cell, preferably a vacuum-deposited organic solar cell, and more preferably a vacuum-deposited bulk heterojunction organic solar cell.

[0088] (2) The solar cell includes a solar cell acceptor material, wherein the solar cell acceptor material is C. 70 ;

[0089] (3) The mass ratio of the solar cell donor material to the solar cell acceptor material is 1:3;

[0090] (4) The solar cell donor material and the solar cell acceptor material are blended by vacuum evaporation.

[0091] (5) The solar cell includes an indium tin oxide conductive glass substrate layer;

[0092] (6) The solar cell includes a molybdenum oxide anode layer;

[0093] (7) The solar cell includes a BCP / Ag cathode layer.

[0094] A fifth aspect of the present invention provides an electrical device including a solar cell according to a fourth aspect of the present invention.

[0095] The sixth aspect of the present invention relates to the compounds of the first aspect of the present invention, their stereoisomers or optical isomers thereof, or the compounds prepared by the method of the second aspect of the present invention, their stereoisomers or optical isomers thereof, or the application of the solar cell donor materials of the third aspect of the present invention in solar cells.

[0096] Optionally, the solar cell is an organic solar cell, more preferably a vacuum-deposited organic solar cell, and even more preferably a vacuum-deposited bulk heterojunction organic solar cell.

[0097] In this invention, unless otherwise specified, wherein:

[0098] The term "alkyl" refers to a group formed by removing one hydrogen atom from an alkane molecule. For example, C 1-6 Alkyl, C 1-4 Alkyl, C 1-2 Alkyl groups; specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0099] The term "alkylene" refers to a divalent group formed by removing one hydrogen atom from an alkyl group; where "alkyl" is defined as described above. For example, C 1-6 Alkylene, C 1-4 Alkylene, C 1-2 Alkylene.

[0100] The term "heteroaryl" refers to an aromatic monocyclic or fused-ring group containing at least one N, O, or S heteroatom. Examples include 5-10 membered heteroaryls, 5-8 membered heteroaryls, 5-7 membered heteroaryls, and 5-6 membered heteroaryls; specific examples include, but are not limited to, porphyrinyl, pyrazolyl, pyrroleyl, thiazolyl, pyridinyl, imidazolyl, quinolinyl, furanyl, and thiophenyl.

[0101] The term "alkylsilyl" refers to a group formed by replacing one, two, or three hydrogen atoms of a silane (SiH4) with an alkyl group and removing one hydrogen atom. The definition of "alkyl" is as described above. For example, a C... 1-6 Alkylsilyl, diC 1-6 Alkylsilane, tri-C 1-6 Alkylsilane, tri-C 1-4 Alkylsilane, tri-C 1-2 Alkylsilane; specific examples include, but are not limited to, trimethylsiloxane, triethylsiloxane, tri-n-propylsiloxane, triisopropylsiloxane, dimethylsiloxane, etc.

[0102] The term "aryl" refers to a monocyclic or fused-ring group that is aromatic. Examples include 5-10-membered aryl, 5-8-membered aryl, 5-7-membered aryl, and 5-6-membered aryl; specific examples include, but are not limited to, phenyl, naphthyl, anthracene, and phenanthrene. "Aromatic ring" refers to a monocyclic or fused-ring compound that is aromatic; examples include 5-10-membered aromatic rings, 5-8-membered aromatic rings, 5-7-membered aromatic rings, and 5-6-membered aromatic rings; specific examples include benzene rings, naphthyl rings, and anthracene rings.

[0103] The term "halogen" refers to fluorine, chlorine, bromine, iodine, astatine, etc.

[0104] The present invention has achieved at least one of the following beneficial effects:

[0105] The compounds, stereoisomers, or optical isomers of the present invention have good stability and excellent optical properties, which are beneficial to improving the photoelectric conversion efficiency of vacuum-deposited organic solar cells. Detailed Implementation

[0106] The embodiments of the present invention will now be clearly and completely described in conjunction with examples. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0107] Example 1: Synthesis of Compound I-1

[0108] Synthesis route:

[0109]

[0110] (1) Synthesis of intermediate compound 1:

[0111] 4-Borate-4',4'-dimethyltriphenylamine (207 mg, 0.52 mmol), 7-bromo-4-aldehyde benzo[C][1,2,5]thiadiazole (104 mg, 0.4 mmol), Pd(PPh3)4 (25 mg, 0.04 mmol), and potassium carbonate (90 mg, 0.6 mmol) were placed in a double-necked flask, purged with argon three times, and then 7 mL of tetrahydrofuran and 1 mL of water were added. The reaction was carried out at 100 °C for 24 h under argon protection. After the reaction was completed, the reaction system was cooled to room temperature, the solvent was removed by rotary evaporation, and the collected product was purified by column chromatography to obtain intermediate compound 1.

[0112] (2) Synthesis of compound I-1:

[0113] Intermediate compound 1 (45 mg, 0.1 mmol), cyanoacetic acid (35 mg, 0.4 mmol), and ammonium acetate (8 mg, 0.1 mmol) were placed in 5 mL of glacial acetic acid and refluxed for 12 h. The reaction system was then cooled to room temperature, poured into water, extracted with dichloromethane, and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate to remove water, and the solvent was removed by rotary evaporation. The collected product was further purified to give compound I-1, with a mass of 40 mg and a yield of 75%.

[0114] pass 1 H NMR, 13Characterization by C10 NMR and Maldi-Tof-MS:

[0115] 1 H NMR (500MHz, CDCl3): δ8.79 (s, 1H), 8.63 (d, J = 10.0Hz, 1H), 7.80-7.78 (m, 2H), 7.15-7.10 (m, 10H), 2.36 (s, 6H) ppm.

[0116] 13 C NMR (150MHz, CDCl3): δ159.19,157.52,154.09,154.02,151.92,151.86,151.84,150.27,144.45,134.55,132.27,130.55,1 30.51,126.30,125.99,125.89,122.28,122.06,121.73,121.72,121.20,121.13,119.85,113.82,112.90,84.25,21.10ppm.

[0117] MALDI-TOF MS(m / z):calcd.for(C 30 H 20 FN5S):501.58; Found:500.86.

[0118] Example 2 Synthesis of Compound I-2

[0119] Synthesis route:

[0120]

[0121] (1) Synthesis of intermediate compound 2:

[0122] 4-Borate-4',4'-dimethyltriphenylamine (207 mg, 0.52 mmol), 7-bromo-4-aldehyde benzo[C][1,2,5]thiadiazole (111 mg, 0.4 mmol), Pd(PPh3)4 (25 mg, 0.04 mmol), and potassium carbonate (90 mg, 0.6 mmol) were placed in a double-necked flask, purged with argon three times, and then 7 mL of tetrahydrofuran and 1 mL of water were added. The reaction was carried out at 100 °C for 24 h under argon protection. After the reaction was completed, the reaction system was cooled to room temperature, the solvent was removed by rotary evaporation, and the collected product was purified by column chromatography to obtain intermediate compound 2.

[0123] (2) Synthesis of compound I-2:

[0124] Intermediate compound 2 (47 mg, 0.1 mmol), cyanoacetic acid (35 mg, 0.4 mmol), and ammonium acetate (8 mg, 0.1 mmol) were placed in 5 mL of glacial acetic acid and refluxed for 12 h. The reaction system was cooled to room temperature, poured into water, and extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate to remove water, and the solvent was removed by rotary evaporation. The collected product was further purified to give compound I-2, with a mass of 40 mg and a yield of 75%.

[0125] pass 1 H NMR, 13 Characterization by C10 NMR and Maldi-Tof-MS:

[0126] 1 H NMR (500MHz, CDCl3): δ8.76 (d, J = 20.0Hz, 2H), 7.52 (d, J = 10.0Hz, 2H), 7.14-7.09 (m, 10H), 2.35 (s, 6H) ppm.

[0127] 13 C NMR (125MHz, CDCl3): δ154.50,152.39,151.62,149.63,144.23,138.26,134.09,132.9 0,131.56,130.19,125.99,124.59,121.63,119.01,113.34,112.35,84.68,20.93ppm.

[0128] MALDI-TOF MS(m / z):calcd.for(C 30 H 20 ClN5S):517.82; Found:517.11.

[0129] Example 3 Synthesis of Compound I-3

[0130] Synthesis route:

[0131]

[0132] (1) Synthesis of intermediate compound 3:

[0133] 4-Borate-4',4'-dimethyltriphenylamine (207 mg, 0.52 mmol), 7-bromo-2-methyl-2H-benzo[d][1,2,3]triazole-4-carboxaldehyde (96 mg, 0.4 mmol), Pd(PPh3)4 (25 mg, 0.04 mmol), and potassium carbonate (90 mg, 0.6 mmol) were placed in a double-necked flask, purged with argon three times, and then 7 mL of tetrahydrofuran and 1 mL of water were added. The mixture was reacted at 100 °C for 24 h under argon protection. After the reaction was completed, the reaction system was cooled to room temperature, the solvent was removed by rotary evaporation, and the collected product was purified by column chromatography to obtain intermediate compound 3.

[0134] pass 1 H NMR and 13 C NMR characterization:

[0135] 1 H NMR (400MHz, CDCl3): δ10.36(s,1H),8.01-7.95(m,3H),7.67(d,1H),7.15-7.05(m,10H),4.63(s,3H),2.34(s,6H)ppm.

[0136] 13 C NMR (100MHz, CDCl3): δ189.49,149.56,144.57,143.67,142.57,138.00,133.62,1 33.51,130.10,129.84,127.98,125.52,124.10,122.25,121.00,43.85,20.50ppm.

[0137] (2) Synthesis of compound I-3:

[0138] Intermediate compound 3 (43 mg, 0.1 mmol), cyanoacetic acid (35 mg, 0.4 mmol), and ammonium acetate (8 mg, 0.1 mmol) were placed in 5 mL of glacial acetic acid and refluxed for 12 h. The reaction system was cooled to room temperature, poured into water, extracted with dichloromethane, and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate to remove water, and the solvent was removed by rotary evaporation. The collected product was further purified to obtain compound I-3.

[0139] pass 1 H NMR and 13 C NMR characterization:

[0140] 1H NMR (500MHz, CDCl3): δ8.60-8.57(m,3H),8.05(d,J=10.5Hz,2H),7.71(d,J=10.0Hz,1H),7.18-7.09(m,10H),4.60(s,3H),2.38(s,6H)ppm.

[0141] 13 C NMR (125MHz, CDCl3): δ152.45,150.03,144.88,144.31,142.50,138.18,133.98,130.16,129. 92,128.37,127.30,125.74,122.63,120.56,118.59,114.38,113.61,80.38,43.79,20.92ppm.

[0142] Example 4 Synthesis of Compound I-4

[0143] Synthesis route:

[0144]

[0145] (1) Synthesis of intermediate compound 4:

[0146] 4-Borate-4',4'-dimethyltriphenylamine (207 mg, 0.52 mmol), 7-bromo-2-butyl-2H-benzo[d][1,2,3]triazole-4-carboxaldehyde (11 mg, 0.4 mmol), Pd(PPh3)4 (25 mg, 0.04 mmol), and potassium carbonate (90 mg, 0.6 mmol) were placed in a double-necked flask, purged with argon three times, and then 7 mL of tetrahydrofuran and 1 mL of water were added. The mixture was reacted at 100 °C for 24 h under argon protection. After the reaction was completed, the reaction system was cooled to room temperature, the solvent was removed by rotary evaporation, and the collected product was purified by column chromatography to obtain intermediate compound 4.

[0147] pass 1 H NMR and 13 C NMR characterization:

[0148] 1 H NMR (400MHz, CDCl3): δ10.40(s,1H),8.03-7.97(m,3H),7.66(d,1H),7.15-7.0 6(m,10H),4.84(t,2H),2.34(s,6H),2.15(m,2H),1.43(m,2H),0.98(t,3H)ppm.

[0149] 13C NMR (100MHz, CDCl3): δ189.46,149.50,144.59,143.41,142.54,137.93,133.60,132.78,130 .10,129.86,128.08,125.54,124.10,122.04,120.94,56.89,32.75,21.34,19.90,12.43ppm.

[0150] (2) Synthesis of compound I-4:

[0151] Intermediate compound 4 (47 mg, 0.1 mmol), cyanoacetic acid (35 mg, 0.4 mmol), and ammonium acetate (8 mg, 0.1 mmol) were placed in 5 mL of glacial acetic acid and refluxed for 12 h. The reaction system was cooled to room temperature, poured into water, extracted with dichloromethane, and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate to remove water, and the solvent was removed by rotary evaporation. The collected product was further purified to obtain compound I-4.

[0152] pass 1 H NMR and 13 C NMR characterization:

[0153] 1 H NMR (500MHz, CDCl3): δ8.61-8.56(m,3H),8.08(d,J=9.0Hz,2H),7.71(d,J=8.0Hz,2H),7.17-7.10(m,10 H),4.80(t,J=7.5Hz,2H),2.37(s,6H),2.18-2.13(m,2H),1.47-1.40(m,2H),1.02(t,J=7.5Hz,3H)ppm.

[0154] 13 C NMR (125MHz, CDCl3): δ152.64,149.98,144.67,144.32,142.18,138.20,133.97,130.16,129.95,128.23 ,127.37,125.76,122.43,120.51,118.68,114.47,113.67,80.18,56.95,32.00,20.92,19.82,13.49ppm.

[0155] Example 5 Synthesis of Compound I-5

[0156] Synthesis route:

[0157]

[0158] (1) Synthesis of intermediate compound 5:

[0159] 4-Borate-4',4'-dimethyltriphenylamine (207 mg, 0.52 mmol), 7-bromo-2-isobutyl-2H-benzo[d][1,2,3]triazole-4-carboxaldehyde (11 mg, 0.4 mmol), Pd(PPh3)4 (25 mg, 0.04 mmol), and potassium carbonate (90 mg, 0.6 mmol) were placed in a double-necked flask, purged with argon three times, and then 7 mL of tetrahydrofuran and 1 mL of water were added. The mixture was reacted at 100 °C for 24 h under argon protection. After the reaction was completed, the reaction system was cooled to room temperature, the solvent was removed by rotary evaporation, and the collected product was purified by column chromatography to obtain intermediate compound 5.

[0160] pass 1 H NMR and 13 C NMR characterization:

[0161] 1 H NMR (400MHz, CDCl3): δ10.41(s,1H),8.00-7.98(m,3H),7.67(d,1H),7.15-7.06(m,10H),4.65(d,2H),2.61(m,1H),2.34(s,6H),1.00(d,6H)ppm.

[0162] 13 C NMR (100MHz, CDCl3): δ189.39,149.48,144.57,143.35,142.62,137.92,133.59,132.61, 130.08,129.83,128.06,125.54,124.09,122.02,120.89,63.98,29.93,20.90,19.95ppm.

[0163] (2) Synthesis of compound I-5:

[0164] Intermediate compound 5 (47 mg, 0.1 mmol), cyanoacetic acid (35 mg, 0.4 mmol), and ammonium acetate (8 mg, 0.1 mmol) were placed in 5 mL of glacial acetic acid and refluxed for 12 h. The reaction system was cooled to room temperature, poured into water, extracted with dichloromethane, and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate to remove water, and the solvent was removed by rotary evaporation. The collected product was further purified to obtain compound I-5.

[0165] pass 1 H NMR and 13 C NMR characterization:

[0166] 1H NMR (500MHz, CDCl3): δ8.60-8.56(m,3H),8.08(d,J=11.0Hz,2H),7.71(d,J=10.0Hz,2H),7. 17-7.11(m,10H),4.60(d,J=9.0Hz,2H),2.59(m,1H),2.38(s,6H),1.03(d,J=8.5Hz,6H)ppm.

[0167] 13 C NMR (125MHz, CDCl3): δ151.60,148.98,143.61,143.29,141.15,137.18,132.96,129.12,128.92,127 .23,126.36,124.76,121.39,119.46,117.67,113.44,112.64,79.15,63.16,28.89,19.89,18.93ppm.

[0168] Example 6 Synthesis of Compound I-6

[0169] Synthesis route:

[0170]

[0171] (1) Synthesis of intermediate compound 6:

[0172] N,N-di-p-tolylbenzofuran-6-amine (626 mg, 2 mmol), nBuLi (0.83 mL, 2.08 mmol), and Sn(Bu)3Cl (25 mg, 0.04 mmol) were placed in a double-necked flask, purged with argon three times, and then 20 mL of tetrahydrofuran was added. The mixture was reacted overnight at -78 °C to room temperature under argon protection. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate compound 6, which was directly added to the next step of the reaction.

[0173] (2) Synthesis of compound I-6:

[0174] Intermediate compound 6 (2.0 mmol), 2-((7-bromobenzo[c][1,2,5]thiadiazol-4-yl)methylene)malonitrile (696 mg, 2.4 mmol), and Pd(PPh3)2Cl2 (70.2 mg, 0.1 mmol) were dissolved in toluene (60 mL). The mixture was refluxed under a nitrogen atmosphere for 17 hours. After cooling, the mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 1:6) as the eluent to give a black solid compound I-6 with a mass of 764 mg and a yield of 73%.

[0175] pass 1 H NMR and mass spectrometry characterization:

[0176] 1 H NMR (500MHz, CDCl3): δ8.78-8.76(m,2H),8.26(s,1H),8.15(d,J=10.0Hz,1H),7.51(d,J=10.0Hz,1H),7.14-7.00(m,10H),2.36(s,6H)ppm.

[0177] MALDI-TOF-MS(m / z):calcd.for(C 37 H 25 N3OS): 522.78; Found: 523.15.

[0178] Example 7 Synthesis of Compound I-7

[0179] Synthesis route:

[0180]

[0181] (1) Synthesis of intermediate compound 7

[0182] N,N-di-p-tolylbenzothiophene-6-amine (820 mg, 2.49 mol), nBuLi (1.34 mL, 2.49 mmol), and Sn(Bu)3Cl (1 mL, 2.74 mmol) were placed in a double-necked flask. After purging with argon three times, 30 mL of tetrahydrofuran was added. The mixture was reacted overnight at -78 °C to room temperature under argon protection. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate compound 7, which was directly added to the next step of the reaction.

[0183] (2) Synthesis of compound I-7:

[0184] Intermediate compound 7 (2.49 mmol), 2-((7-bromobenzo[c][1,2,5]thiadiazol-4-yl)methylene)malonitrile (866.3 mg, 2.99 mmol), and Pd(PPh3)2Cl2 (88.4 mg, 0.12 mmol) were dissolved in toluene (80 mL). The mixture was refluxed under nitrogen for 17 hours. After cooling, the mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by vortexing. The crude product was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 1:8) as the eluent to give a black solid I-7 with a mass of 1.06 g and a yield of 79%.

[0185] pass 1 H NMR and mass spectrometry characterization:

[0186] 1 H NMR (500MHz, CDCl3): δ8.77-8.70(m,3H),7.90(d,J=10.0Hz,1H),7.70(d,J=10.0Hz,1H),7.14-7.06(m,10H),2.37(s,6H)ppm.

[0187] MALDI-TOF-MS(m / z):calcd.for(C 32 H 21 N5S2):539.12; Found:539.70.

[0188] Example 8 Synthesis of Compound I-8

[0189] Synthesis route:

[0190]

[0191] (1) Synthesis of intermediate compound 8:

[0192] 4-(furan-2-yl)-N,N-di-p-tolylaniline (678 mg, 2 mmol), nBuLi (1.3 mL, 2.04 mmol), and Sn(Bu)3Cl (0.61 mL, 2.08 mmol) were placed in a double-necked flask, purged with argon three times, and then 20 mL of tetrahydrofuran was added. The mixture was reacted overnight at -78 °C to room temperature under argon protection. After the reaction was completed, the solvent was removed by rotary evaporation to obtain reaction intermediate 8, which was directly added to the next step of the reaction.

[0193] (2) Synthesis of compound I-8:

[0194] Intermediate compound 8 (2.0 mmol), 2-((7-bromobenzo[c][1,2,5]thiadiazol-4-yl)methylene)malonitrile (696 mg, 2.4 mmol), and Pd(PPh3)2Cl2 (70.2 mg, 0.1 mmol) were added to toluene (60 mL) and stirred. The mixture was refluxed under a nitrogen atmosphere for 18 hours. After cooling, the mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 1:5) as the eluent to give green solid I-8 with a mass of 780 mg and a yield of 71%.

[0195] pass 1 H NMR and mass spectrometry characterization:

[0196] 1H NMR (500MHz, CDCl3): δ8.82-8.78(m,2H),8.14(d,J=10.0Hz,1H),8.06(d,J=5.0Hz,1H),7.65(d,J=10.0Hz,2H),7.13-7.04(m,10H),2.34(s,6H)ppm.

[0197] MALDI-TOF-MS(m / z):calcd.for(C 34 H 25 N5OS):549.16; Found:550.69.

[0198] Example 9 Synthesis of Compound I-9

[0199] Synthesis route:

[0200]

[0201] (1) Synthesis of intermediate compound 9:

[0202] 4-(thiophen-2-yl)-N,N-di-p-tolylaniline (625 mg, 2 mmol), nBuLi (1.0 mL, 2.04 mmol), and Sn(Bu)3Cl (0.5 mL, 2.08 mmol) were placed in a double-necked flask, purged with argon three times, and then 20 mL of tetrahydrofuran was added. The mixture was reacted overnight at -78 °C to room temperature under argon protection. After the reaction was completed, the solvent was removed by rotary evaporation to obtain reaction intermediate 9, which was directly added to the next step of the reaction. (2) Synthesis of compound I-9:

[0203] Intermediate compound 9 (2.0 mmol), 2-((7-bromobenzo[c][1,2,5]thiadiazol-4-yl)methylene)malonitrile (696 mg, 2.4 mmol), and Pd(PPh3)2Cl2 (70.2 mg, 0.1 mmol) were added to toluene (60 mL) and stirred. The mixture was refluxed under a nitrogen atmosphere for 16 hours. After cooling, the mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 1:8) as the eluent to give a black solid compound I-9 with a mass of 916 mg and a yield of 81%.

[0204] pass 1 H NMR and mass spectrometry characterization:

[0205] 1H NMR (500MHz, CDCl3): δ8.77-8.74(m,2H),8.33(d,J=5.0Hz,1H),7.96(d,J=10.0Hz,1H),7.53(d, J=10.0Hz,2H),7.36(d,J=5.0Hz,1H),7.11(d,J=10.0Hz,4H),7.06-7.04(m,6H),2.34(s,6H)ppm.

[0206] MALDI-TOF-MS(m / z):calcd.for(C 34 H 23 N5S2):565.14;Found:564.52;

[0207] Example 10 Synthesis of Compound I-10

[0208] Synthesis route:

[0209]

[0210] (1) Synthesis of intermediate compound 10:

[0211] Prepare a 150 mL two-necked flask and dry it at 70 °C for 30 min. Weigh 4-boronate-4',4'-dimethyltriphenylamine (500.0 mg, 1.25 mmol), 5-bromo-2-furfural (218.7 mg, 1.25 mmol), anhydrous potassium carbonate (862.5 mg, 6.25 mmol), and tetra(triphenylphosphine)palladium (144.4 mg, 0.125 mmol) into the flask. Repeatedly evacuate and purge with nitrogen three times using a double-row tube system to ensure that the reaction system is oxygen-free. A 50 mL mixture of 1,4-dioxane and water (mass ratio 9:1) was deoxygenated by purging with nitrogen for 30 min. The solution was then added to a flask to completely dissolve the solid. The mixture was slowly heated to 80 °C and reacted overnight at this temperature with stirring. The reaction was quenched by adding purified water. The product was extracted with dichloromethane, and the solvent was removed by rotary evaporation. The collected product was purified by silica gel column chromatography using petroleum ether / dichloromethane (volume ratio 1:1) as the eluent. The collected orange solid was intermediate compound 10, with a mass of 348.8 mg and a yield of 76%.

[0212] pass 1 H NMR and 13 C NMR characterization:

[0213] 1H NMR (400MHz, CDCl3): δ10.02(s,1H),7.93-7.90(m,2H),7.73-7.70(m,2H),7.50-7.47(m,2H),7.12-7.03(m,10H),2.33(s,6H)ppm.

[0214] 13 C NMR (100MHz, CDCl3): δ192.01,148.98,146.90,144.96,134.67,133.40,131.88,130.47,130.18,128.01,126.90,125.29,121.96,21.01ppm.

[0215] (2) Synthesis of compound I-10

[0216] A 150 mL round-bottom flask was dried at 70 °C for 30 min. Intermediate compound 10 (200.0 mg, 0.54 mmol) and 3-(dicyanomethylene)indene-1-one (105.3 mg, 0.58 mmol) were weighed into the flask. The mixture was repeatedly evacuated and purged with nitrogen three times using a double-row tube system to ensure an oxygen-free reaction system. 30 mL of chloroform was added to the flask to completely dissolve the solid. Ultra-dry pyridine (0.1 mL, 1.25 mmol) was added dropwise. The temperature was slowly raised to 65 °C and reacted overnight with stirring. The reaction was cooled to room temperature, quenched with purified water, and extracted with dichloromethane. The solvent was removed by rotary evaporation. The collected product was purified by silica gel column chromatography using petroleum ether / dichloromethane (volume ratio 1:4) as the eluent. The resulting brown substance was compound I-10, with a mass of 180.5 mg and a yield of 61%.

[0217] pass 1 H NMR, 13 Characterization by C10 NMR and MALDI-TOF MS:

[0218] 1 H NMR (400MHz, CDCl3): δ8.84(s,1H),8.68(d,J=7.7Hz,1H),7.95-7.88(m,1H),7.83(d,J=4.2Hz,1H),7.74(dd,J=9.1,4.3Hz,2H), 7.62(d,J=8.7Hz,2H),7.38(d,J=3.8Hz,1H),7.13(d,J=8.3Hz,4H),7.06(d,J=8.2Hz,4H),6.99(d,J=8.2Hz,2H),2.35(s,6H)ppm.

[0219] 13 C NMR (150MHz, CDCl3): δ188.36,161.70,160.75,150.53,146.95,144.00,140.01,138.11,138.02,136.92,135.36,134.9 6,134.33,130.21,127.78,125.77,125.22,124.84,123.64,121.44,121.35,120.52,114.83,114.73,68.75,20.94ppm.

[0220] MALDI-TOF-MS(m / z):calcd.for(C 37 H 25 N3OS):559.7; Found:558.5.

[0221] Example 11 Synthesis of Compound I-11

[0222] Synthesis route:

[0223]

[0224] (1) Synthesis of intermediate compound 11:

[0225] Prepare a 150 mL two-necked flask and dry it at 70 °C for 30 min. Weigh 4-boronic acid ester-4',4'-dimethyltriphenylamine (500.0 mg, 1.25 mmol), 5-bromothiophene-2-carboxaldehyde (237.5 mg, 1.25 mmol), anhydrous potassium carbonate (862.5 mg, 6.25 mmol), and tetra(triphenylphosphine)palladium (144.4 mg, 0.125 mmol) into the flask. Repeatedly evacuate and purge with nitrogen three times using a double-row tube system to ensure that the reaction system is oxygen-free. A 50 mL mixture of 1,4-dioxane and water (volume ratio 9:1) was purged with nitrogen for 30 min to remove oxygen. The solution was then added to a flask to completely dissolve the solid. The mixture was slowly heated to 80 °C and reacted overnight at this temperature with stirring. The reaction was quenched by adding purified water. The product was extracted with dichloromethane, and the solvent was removed by rotary evaporation. The collected product was purified by silica gel column chromatography using petroleum ether / dichloromethane (volume ratio 1:1) as the eluent, yielding a yellow solid, intermediate compound 11, with a mass of 363.9 mg and a yield of 76%.

[0226] pass 1 H NMR and 13 C NMR characterization:

[0227] 1H NMR (400MHz, CDCl3): δ8.19(s,1H),7.76-7.72(m,2H),7.15-6.95(m,12H),2.35(s,6H)ppm.

[0228] 13 C NMR (100MHz, CDCl3): δ182.67,155.01,149.66,144.53,141.15,137.91,133.82,131.57,130.24,127.26,125.53,122.69,121.19,21.01ppm.

[0229] (2) Synthesis of compound I-11:

[0230] A 150 mL round-bottom flask was dried at 70 °C for 30 min. Intermediate compound 11 (200.0 mg, 0.52 mmol) and 3-(dicyanomethylene)indene-1-one (101.4 mg, 0.58 mmol) were weighed into the flask. The mixture was repeatedly evacuated and purged with nitrogen three times using a double-row tube system to ensure an oxygen-free reaction system. 30 mL of chloroform was added to the flask to completely dissolve the solid. Ultra-dry pyridine (0.1 mL, 1.25 mmol) was added dropwise. The temperature was slowly raised to 65 °C and reacted overnight with stirring. The reaction was cooled to room temperature, quenched with purified water, and extracted with dichloromethane. The solvent was removed by rotary evaporation. The collected product was purified by silica gel column chromatography using petroleum ether / dichloromethane (volume ratio 1:4) as the eluent. The resulting black substance was compound I-11, with a mass of 203.3 mg and a yield of 65%.

[0231] pass 1 H NMR, 13 Characterization by C10 NMR and MALDI-TOF MS:

[0232] 1 H NMR (400MHz, CDCl3): δ8.86 (s, 1H), 8.68 (dd, J = 6.3, 1.9Hz, 1H), 8.56 (s, 1H), 7.93-7.8 6(m,1H),7.79-7.66(m,4H),7.16(d,J=8.1Hz,4H),7.12-6.91(m,7H),2.38(s,6H)ppm.

[0233] 13C NMR (150MHz, CDCl3): δ187.50,163.61,161.09,150.75,150.51,143.86,139.87,137.21,134.66,134.48,134.15,1 32.53,130.26,128.40,125.89,125.00,123.43,121.30,120.04,119.86,115.06,114.79,110.92,68.20,20.96ppm.

[0234] MALDI-TOF-MS(m / z):calcd.for(C 37 H 25 N3O2): 543.6; Found: 542.6.

[0235] Example 12 Synthesis of Compound I-12

[0236] Synthesis route:

[0237]

[0238] (1) Synthesis of intermediate compound 12:

[0239] 8-Isobutyl-6-(tributyltin-2-(triisopropylsilyl-8H-thiophene[2',3':4,5]thiophene[3,2-b]thiophene[2,3-d]pyrrole (736 mg, 1.00 mmol), 7-bromobenzo[c][1,2,5]thiadiazole-4-carboxaldehyde (280 mg, 1.15 mmol) and Pd(PPh3)2Cl2 (40 mg, 0.06 mmol) were added to toluene (60 mL) solvent and stirred. The mixture was refluxed under a nitrogen atmosphere for 3 hours. After cooling, the mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 1:1) as the eluent, yielding a black solid as intermediate compound 12 with a mass of 400 mg and a yield of 59%.

[0240] pass 1 H NMR, 13 C NMR and mass spectrometry characterization:

[0241] 1H NMR (400MHz, CDCl3): δ10.65(s,1H),8.51(s,1H),8.18(d,J=7.7Hz,1H),7.93(d,J=7.6Hz,1H),7.41(s,1H),4 .20(d,J=7.5Hz,2H),2.44-2.37(m,1H),1.45-1.38(m,3H),1.18(d,J=7.4Hz,18H),1.08(d,J=6.6Hz,6H)ppm.

[0242] 13 C NMR (100MHz, CDCl3): δ188.39,154.00,152.17,145.23,142.68,138.28,136.25,135.58,134.47,133 .16,128.87,128.39,124.44,122.32,119.83,117.38,115.22,55.33,30.52,20.37,18.65,11.91ppm.

[0243] HRMS(ESI)found:m / z 610.14[M+H] + ;Calcd.for C 30 H 35 N3OS4Si:m / z 609.14.

[0244] (2) Synthesis of compound I-12:

[0245] A mixture of intermediate compound 12 (100 mg, 0.17 mmol), malononitrile (13.2 mg, 0.20 mmol), and 5 drops of triethylamine was stirred in chloroform solvent (5 mL) at room temperature under a nitrogen atmosphere for 30 minutes. The solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in dichloromethane and precipitated with methanol. The precipitate was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 2:1) as the eluent to obtain a black solid, compound I-12, with a mass of 98 mg and a yield of 90%.

[0246] pass 1 H NMR, 13 C NMR and mass spectrometry characterization:

[0247] 1H NMR (400MHz, CDCl3): δ8.78-8.76(m,2H),8.55(s,1H),7.96(d,J=8.4Hz,1H),7.44(s,1H),4.24(d,J =7.5Hz,2H),2.45-2.41(m,1H),1.44-1.41(m,3H),1.21(d,J=7.4Hz,18H),1.12(d,J=6.6Hz,6H)ppm.

[0248] 13 C NMR (100MHz, CDCl3): δ154.47,151.45,150.61,145.36,143.30,138.94,137.20,135.51,134.36,130.49,128.73 ,127.98,122.25,121.09,119.97,117.38,115.47,114.26,113.51,79.57,55.14,30.31,20.19,18.47,11.72ppm.

[0249] HRMS(ESI)found:m / z 658.16[M+H] + ;Calcd.for C 33 H 35 N5S4Si:m / z 657.15.

[0250] Example 13 Synthesis of Compound I-13

[0251] Synthesis route:

[0252]

[0253] (1) Synthesis of intermediate compound 13:

[0254] 8-Isobutyl-6-(tributyltin-2-(triisopropylsilyl-8H-thiophene[2',3':4,5]thiophene[3,2-b]thiophene[2,3-d]pyrrole (736 mg, 1.00 mmol), 7-bromo-6-fluorobenzo[c][1,2,5]thiadiazole-4-carboxaldehyde (300 mg, 1.15 mmol) and Pd(PPh3)2Cl2 (40 mg, 0.06 mmol) were added to toluene (60 mL) solvent and stirred. The mixture was refluxed under a nitrogen atmosphere for 3 hours. After cooling, the mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography with dichloromethane / petroleum ether (volume ratio 1:1) as the eluent to obtain a black solid, which was intermediate compound 13, with a mass of 380 mg and a yield of 55%.

[0255] pass 1 H NMR, 13 C NMR and mass spectrometry characterization:

[0256] 1 H NMR (400MHz, CDCl3): δ10.60(d,J=1.7Hz,1H),8.46(s,1H),8.04(d,J=12.5Hz,1H),7.41(s,1H),4.14(d ,J=7.5Hz,2H),2.40-2.32(m,1H),1.46-1.39(m,3H),1.19(d,J=7.4Hz,18H),1.05(d,J=6.6Hz,6H)ppm.

[0257] 13 C NMR (100MHz, CDCl3): δ187.04, 158.50, 155.97, 152.92 (d, J = 9.9Hz, 1C), 151.13, 144.62, 142.95, 138.55, 136 .45,129.42,128.89,128.25,122.67,122.38,120.17,117.09,116.28,55.20,30.50,20.37,18.66,11.91ppm.

[0258] HRMS(ESI) found: m / z 627.10 [M + ];Calcd.for C 30 H 34 FN3OS4Si:m / z 627.13.

[0259] (2) Synthesis of compound I-13:

[0260] A mixture of intermediate compound 13 (100 mg, 0.15 mmol), malononitrile (13.2 mg, 0.20 mmol), and 5 drops of triethylamine was stirred in chloroform solvent (5 mL) at room temperature under a nitrogen atmosphere for 30 minutes. The solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in dichloromethane and precipitated with methanol. The precipitate was purified by silica gel column chromatography using dichloromethane / petroleum ether (volume ratio 2:1) as the eluent to obtain a black solid, compound I-13, with a mass of 85 mg and a yield of 85%.

[0261] pass 1 H NMR, 13 C NMR and mass spectrometry characterization:

[0262] 1 H NMR (400MHz, CDCl3): δ8.65(s,1H),8.60(d,J=13.6Hz,1H),7.43(s,1H),4.21(d,J=7.5Hz,2 H),2.40-2.37(m,1H),1.46-1.39(m,3H),1.19(d,J=7.4Hz,18H),1.08(d,J=6.6Hz,6H)ppm.

[0263] 13 C NMR (100MHz, CDCl3): δ157.77,155.25,151.69,151.20,149.87,144.98,143.82,139.53,137.96,128.92,128.06 ,123.75,120.50,120.17,118.31,117.24,116.43,113.84,113.07,80.68,55.21,30.44,20.32,18.60,11.86ppm.

[0264] HRMS(ESI)found:m / z 676.15[M+H] + ;Calcd.for C 33 H 34 FN5S4Si:m / z 675.14.

[0265] Example 14 Synthesis of Compound I-14

[0266] Synthesis route:

[0267]

[0268] (1) Synthesis of intermediate compound 14:

[0269] 4,5-Diisobutyl-2-(tributyltinyl)-4,5-dihydrothieno[2”,3”:4’,5’]pyrrolo[2’,3’:4,5]thieno[3,2-b]indole (670 mg, 1.00 mmol), 7-bromobenzo[c][1,2,5]thiadiazole-4-carboxaldehyde (243 mg, 1.00 mmol) and Pd(PPh3)2Cl2 (35 mg, 0.05 mmol) were added to toluene (60 mL) solvent and stirred. The mixture was refluxed under a nitrogen atmosphere for 3 hours. After cooling, the reaction mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water. The solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by silica gel column chromatography with dichloromethane / petroleum ether (volume ratio 2:1) as the eluent to obtain a black solid, which was intermediate compound 14, with a mass of 298 mg and a yield of 55%.

[0270] pass 1 H NMR and mass spectrometry characterization:

[0271] 1 H NMR (400MHz, CDCl3): δ10.70(s,1H),8.60(s,1H),8.24(d,J=7.6Hz,1H),7.98(d,J=7.6Hz,1H),7.76–7.71(m,1H),7.50–7.44(m,1H),7.36–7. 30(m,1H),7.26–7.20(m,1H),4.38(d,J=7.7Hz,2H),4.32(d,J=7.8Hz,2H),2.43–2.32(m,2H),1.00(d,J=6.6Hz,6H),0.92(d,J=6.6Hz,6H)ppm.

[0272] MALDI-TOF-MS(m / z):calcd.for(C 29 H 26 N4OS3):542.13; Found:541.55.

[0273] (2) Synthesis of compound I-14:

[0274] A mixture of intermediate compound 14 (109 mg, 0.20 mmol), malononitrile (20 mg, 0.30 mmol), and 5 drops of triethylamine was stirred in chloroform solvent (5 mL) at room temperature under a nitrogen atmosphere for 30 minutes. The solvent was removed by rotary evaporation, and the precipitate was directly precipitated with methanol. The precipitate was purified by silica gel column chromatography using dichloromethane / petroleum ether (2:1 v / v) as the eluent to give a reddish-brown solid, compound I-14, with a mass of 85 mg and a yield of 72%.

[0275] pass 1 H NMR and mass spectrometry characterization:

[0276] 1 H NMR (400MHz, CDCl3): δ8.77(d,J=6.6Hz,2H),8.59(s,1H),7.98–7.90(m,1H),7.72(s,1H),7.50–7.43(m,1H),7.37–7.30(m,1H),7 .27–7.19(m,1H),4.36(d,J=7.7Hz,2H),4.31(d,J=7.7Hz,2H),2.44–2.30(m,2H),1.00(d,J=6.6Hz,6H),0.92(d,J=6.6Hz,6H)ppm.

[0277] MALDI-TOF-MS(m / z):calcd.for(C 32 H 26 N6S3):590.14;Found:589.33;

[0278] Example 15 Synthesis of Compound I-15

[0279] Synthesis route:

[0280]

[0281] (1) Synthesis of intermediate compound 15:

[0282] 4,5-Diisobutyl-2-(tributyltinyl)-4,5-dihydrothiopheno[2”,3”:4',5']pyrrolo[2',3':4,5]thiopheno[3,2-b]indole (670 mg, 1.00 mmol), 7-bromo-6-fluorobenzo[c][1,2,5]thiadiazole-4-carboxaldehyde (262 mg, 1.00 mmol), and Pd(PPh3)2Cl2 (35 mg, 0.05 mmol) were added. The mixture was stirred in toluene (60 mL) and refluxed under a nitrogen atmosphere for 3 hours. After cooling, the reaction mixture was poured into water and extracted with dichloromethane. The organic phase was dried over MgSO4 to remove water, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography with dichloromethane / petroleum ether (volume ratio 2:1) as the eluent to obtain a black solid, which was intermediate compound 15, with a mass of 336 mg and a yield of 60%.

[0283] pass 1 H NMR and mass spectrometry characterization:

[0284] 1H NMR (400MHz, CDCl3): δ10.75(s,1H),8.61(s,1H),8.23–8.13(m,1H),7.73(s,1H),7.52–7.43(m,1H),7.36–7.31(m,1H),7.27– 7.17(m,1H),4.38(d,J=7.7Hz,2H),4.32(d,J=7.7Hz,2H),2.43–2.32(m,2H),0.99(d,J=6.6Hz,6H),0.93(d,J=6.6Hz,6H)ppm.

[0285] MALDI-TOF-MS(m / z):calcd.for(C 29 H 25 FN4OS3):560.12; Found:559.46.

[0286] (2) Synthesis of compound I-15:

[0287] A mixture of intermediate compound 15 (112 mg, 0.20 mmol), malononitrile (20 mg, 0.30 mmol), and 5 drops of triethylamine was stirred in chloroform solvent (5 mL) at room temperature under a nitrogen atmosphere for 30 minutes. The solvent was removed by rotary evaporation, and the precipitate was directly precipitated with methanol. The precipitate was purified by silica gel column chromatography using dichloromethane / petroleum ether (2:1 v / v) as the eluent to give a brown solid, compound I-15, with a mass of 90 mg and a yield of 74%.

[0288] pass 1 H NMR and mass spectrometry characterization:

[0289] 1 H NMR (400MHz, CDCl3): δ8.69(s,1H),8.68–8.54(m,2H),7.68(s,1H),7.48(s,1H),7.40–7.30(m,1H),7.27–7.18(m,1 H), 4.36 (d, J = 7.6Hz, 2H), 4.31 (d, J = 7.7Hz, 2H), 2.44–2.31 (m, 2H), 1.01 (d, J = 6.6Hz, 6H), 0.93 (d, J = 6.6Hz, 6H) ppm.

[0290] MALDI-TOF-MS(m / z):calcd.for(C 32 H 25 FN6S3):608.13;Found:607.21;

[0291] Performance testing

[0292] (1) Thermal stability analysis: Using an SDT Q600 thermogravimetric analyzer from TA Instruments (USA), the compound was heated from room temperature to 800℃ at a constant rate over 120 min under a nitrogen atmosphere, and then allowed to cool naturally. The decomposition temperature (Td) corresponding to a 5% weight loss of the compound was recorded, and the results are shown in Table 1.

[0293] (2) Ultraviolet-visible absorption spectroscopy test: The compound in chloroform solution (concentration of 10) was tested using a Varian Cary 5000 ultraviolet-visible spectrophotometer. -5 The absorption peak values ​​were measured using dichloromethane solvent (mol / L), with a blank control in the range of 200-800 nm. The results are shown in Table 1.

[0294] Compound A:

[0295] Compound B:

[0296] Compound C:

[0297] Table 1. Results of thermal stability and UV-Vis absorption spectroscopy tests

[0298]

[0299]

[0300] As shown in Table 1:

[0301] The decomposition temperatures of compounds I-1 to I-15 are all above 270°C, indicating that the compounds of the present invention possess high thermal stability and are suitable as donor materials for the fabrication of organic solar cells using vacuum thermal evaporation. Specifically, compared to compound A, compounds I-1, I-2, and I-3 exhibit higher thermal stability; compared to compound B, compounds I-14 and I-15 exhibit higher thermal stability; and compared to compound C, compounds I-1 to I-11 exhibit higher thermal stability.

[0302] Compared with compound A, the absorption peaks of compounds I-1 and I-2 of the present invention both exhibit a red shift, indicating that compounds I-1 and I-2 of the present invention have stronger absorption of visible light and near-infrared light and better optical properties than compound A.

[0303] Compared with compound B, the absorption peaks of compounds I-14 and I-15 of the present invention both exhibit a red shift, indicating that compounds I-14 and I-15 of the present invention have stronger absorption of visible light and near-infrared light and better optical properties than compound B.

[0304] Compared with compound C, the absorption peaks of compounds I-1 to I-11 of the present invention all exhibit a red shift, indicating that compounds I-1 to I-11 of the present invention have stronger absorption of visible light and near-infrared light and better optical properties than compound C.

[0305] (3) Photovoltaic performance testing:

[0306] 1) Etch the ITO conductive glass with zinc powder and hydrochloric acid. The etched ITO conductive glass (sheet resistance of 7Ω / sq) is then ultrasonically cleaned with glass cleaning solution, deionized water, acetone and isopropanol for 15 minutes in sequence. After that, it is dried with a nitrogen gun and placed in a forced-air drying oven at 150℃ for 5 minutes. Then, the ITO conductive glass is placed in an ultraviolet-ozone cleaner for 15 minutes and transferred to a glove box for later use.

[0307] 2) A 10 nm thick MoO3 layer was deposited on the surface of ITO conductive glass as an anode buffer layer using vacuum thermal evaporation, with a background vacuum of 2.0 × 10⁻⁶. -5 Pa, evaporation rate is 0.2 nm / s;

[0308] 3) Using compounds as donor materials, with C 70 Using a vacuum dual-source co-evaporation method, a hybrid photoactive layer (Compounds:C) was prepared on the surface of a MoO3 anodic buffer layer as the acceptor. 70 The thickness is 80 nm, and the background vacuum is 2.0 × 10⁻⁶. -5 Pa, the evaporation rate ratio of donor to acceptor is 1:1-1:5, and the total evaporation rate is 1.0 nm / s;

[0309] 4) The photoactive layer Compounds:C is deposited using a vacuum thermal evaporation method. 70 A 5 nm thick layer of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (Bathocuproine, BCP) was deposited on the surface as an exciton blocking layer, with a background vacuum of 2.0 × 10⁻⁶. -5 Pa, with an evaporation rate of 0.1 nm / s. Finally, at 2.0 × 10 -5 A 100 nm thick Ag electrode was deposited under a background vacuum of Pa.

[0310] 5) Organic solar cells were tested using a Kiethley 2420 current source meter at AM 1.5G 100mW / cm². 2 The current density-voltage (JV) curve under simulated sunlight irradiation was used to obtain the photovoltaic performance parameters of the cell—photovoltaic conversion efficiency (PCE) and open-circuit voltage (V)—using the testing software integrated into the current source meter. oc ), short-circuit current density (J sc ) and fill factor (FF).

[0311] The results are shown in Table 2.

[0312] Table 2 Photovoltaic performance test results

[0313]

[0314]

[0315] As shown in Table 2, the photovoltaic conversion efficiencies of the organic solar cells fabricated using compounds I-1 to I-15 of the present invention are all above 6.3%, indicating that the compounds of the present invention have high photovoltaic conversion efficiencies and are suitable as donor materials for the preparation of organic solar cells using the vacuum thermal evaporation method. Furthermore, compared with compound C, the photovoltaic conversion efficiencies of the organic solar cells fabricated using compounds I-1 to I-11 of the present invention are significantly higher.

[0316] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. The compound represented by Formula I, Ⅰ in, D is selected from and Wherein, R1 and R2 are selected from methyl groups; R5 and R6 are each independently selected from C4. 1-6 Alkyl group; R3 is selected from furanyl, thiophene, or R3 forms furanyl or thiophene with the carbon atom attached to the benzene ring and the adjacent carbon atom, or R3 is absent; R4 is a three-carbon group. 1-6 Alkyl silyl group, or R4, forms a benzene ring with a carbon atom attached to a five-membered ring and a carbon atom in the adjacent position; Y is selected from S and N; m is 0 or 1; π is selected from any of the following groups: ， Wherein, X2 is selected from H and halogens; X3 is selected from methyl and isobutyl; A is ; Furthermore, the compound is not one of the following: 。 2. The compound according to claim 1, wherein, D is selected from and ; Wherein, R1 and R2 are selected from methyl; R5 and R6 are each independently selected from methyl and isobutyl; R3 is selected from , R3 may form a furanyl or thiophene group with the carbon atom attached to the benzene ring and the adjacent carbon atom, or R3 may not exist; R4 may be a triisopropylsilyl group, or R4 may form a benzene ring with the carbon atom attached to the five-membered ring and the adjacent carbon atom; Y may be selected from S and N; m may be 0 or 1.

3. The compound according to claim 1, wherein, D is selected from , , , , , and .

4. The compound according to claim 1, wherein, π is selected from any of the following groups: ， X2 is selected from H, F and Cl; X3 is selected from methyl and isobutyl.

5. Compounds represented by formulas I-1 to I-3, I-5 to I-9, and I-11 to I-15 as follows: 。 6. A method for preparing the compound according to any one of claims 1 to 5, wherein the method is method one, method two, or method three; Method 1 includes the following steps: The compound represented by formula M and the compound represented by formula B undergo a coupling reaction in a solvent to give the compound represented by formula C, as shown in the following reaction formula: ； The compound represented by formula C undergoes a condensation reaction with a compound containing the A group in a solvent to give the compound represented by formula I, as shown in the following reaction formula: ； The second method includes the following steps: The compound represented by formula N undergoes a lithiation reaction and a lithium halide exchange reaction with tributyltin chloride in a solvent to give the compound represented by formula F, as shown in the following reaction formula: ； The compound represented by formula F undergoes a coupling reaction with the compound represented by formula H in a solvent to give the compound represented by formula I, as shown in the following reaction formula: ； Method 3 includes the following steps: The compound represented by formula F undergoes a coupling reaction with the compound represented by formula B in a solvent to give the compound represented by formula C, as shown in the following reaction formula: ； The compound represented by formula C undergoes a condensation reaction with a compound containing the A group in a solvent to give the compound represented by formula I, as shown in the following reaction formula: ； in, The definitions of D, π, and A groups are as described in any one of claims 1 to 5.

7. The method according to claim 6, characterized in that... One or more of the following: 1) In Method 1, the coupling reaction uses Pd(PPh3)4 catalyst; 2) In Method 1, the molar ratio of the compound represented by Formula M to the compound represented by Formula B is 1:2-1:4; 3) In Method 1, the solvent used in the coupling reaction is selected from one or more of tetrahydrofuran, water, and toluene; 4) In Method 1, the coupling reaction temperature is 90-130℃; 5) In Method 1, Method 2 and / or Method 3, the coupling reaction time is 16-30 h; 6) In Method 1, the solvent used for the condensation reaction is acetic acid; 7) In Method 1, the temperature of the condensation reaction is 10-30℃; 8) In Method 1, the condensation reaction time is 10-30 hours; 9) In Method 2, the solvent used for the lithiation reaction and the lithium halide exchange reaction is tetrahydrofuran; 10) In Method 2, the temperature for the lithiation reaction and the lithium halide exchange reaction is -60 to -80°C; 11) In Method 2, the time for the lithiation reaction and the lithium halide exchange reaction is 10-30 h; 12) In Method 2 and / or Method 3, the coupling reaction uses Pd(PPh3)2Cl2 catalyst; 13) In Method Two, the molar ratio of the compound represented by Formula F to the compound represented by Formula H is 1:3-1:5; 14) In Method 2 and / or Method 3, the solvent used in the coupling reaction is selected from one or more of tetrahydrofuran, dioxane and toluene; 15) In Method 2 and / or Method 3, the coupling reaction temperature is 100-150℃; 16) In method three, the molar ratio of the compound represented by formula F to the compound represented by formula B is 1:3-1:5; 17) In method three, the solvent used for the condensation reaction is chloroform; 18) In method three, the temperature of the condensation reaction is 15-35℃; 19) In method three, the condensation reaction time is 5-10 hours.

8. A solar cell donor material comprising the compound of any one of claims 1 to 5, or the compound prepared by the method of claim 6 or 7.

9. The solar cell donor material according to claim 8, wherein, The solar cell donor material is an organic solar cell donor material.

10. The solar cell donor material according to claim 8 or 9, wherein, The solar cell donor material is a vacuum-deposited organic solar cell donor material.

11. A solar cell comprising the compound of any one of claims 1 to 5, or the compound prepared by the method of claim 6 or 7, or the solar cell donor material of any one of claims 8 to 10.

12. The solar cell according to claim 11, characterized in that... One or more of the following: (1) The solar cell is an organic solar cell; (2) The solar cell includes a solar cell acceptor material, wherein the solar cell acceptor material is C. 70 ; (3) The mass ratio of the solar cell donor material to the solar cell acceptor material is 1:3; (4) The solar cell donor material and the solar cell acceptor material are blended by vacuum evaporation. (5) The solar cell includes an indium tin oxide conductive glass substrate layer; (6) The solar cell includes a molybdenum oxide anode layer; (7) The solar cell includes a BCP / Ag cathode layer.

13. The solar cell according to claim 12, wherein, The solar cell is a vacuum-deposited organic solar cell.

14. The solar cell according to claim 12, wherein, The solar cell is a vacuum-deposited bulk heterojunction organic solar cell.

15. An electrical device comprising a solar cell as described in any one of claims 11 to 14.

16. The use of the compound of any one of claims 1 to 5, or the compound prepared by the method of claim 6 or 7, or the solar cell donor material of any one of claims 8 to 10 in a solar cell.

17. The application according to claim 16, wherein, The solar cell is an organic solar cell.

18. The application according to claim 16, wherein, The solar cell is a vacuum-deposited organic solar cell.

19. The application according to claim 16, wherein, The solar cell is a vacuum-deposited bulk heterojunction organic solar cell.

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