A method for preparing asymmetric diaryltrithiophene / selenophene small molecule materials and their applications

Abstract

This invention belongs to the field of molecular synthesis and materials technology, and discloses a method for preparing small molecule materials based on benzothiophene-benzodithiophene (DBDTT) and benzoselenophene-benzodiselenophene, as well as their applications. The method includes: using 1-chloro-2-iodobenzene or 1-chloro-2-bromobenzene and trimethylethynylsilane as raw materials, after a stalk coupling reaction, removing the TMS (trimethylsilyl group) with potassium hydrofluoric acid to obtain a key intermediate; using S8 or Se as a sulfur source or selenium source, and potassium carbonate as a base, a series of fused-ring thiophene / selenophene small molecule materials are synthesized through a cascade cyclization reaction. The substrates of this invention are simple to synthesize, the raw materials are inexpensive and readily available; no metals are involved; the reaction can be carried out under air conditions; the reaction efficiency is high, with three rings fused simultaneously in a single step; the yield is moderate, and even at a large scale (10 mmol), the yield can still reach 58%. Therefore, this method is suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of molecular synthesis and materials technology, and relates to a method for preparing asymmetric diaryltrithiophene / selenophene small molecule materials and their applications. Background Technology

[0002] Organic semiconductor devices mainly include organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OPVs). Currently, OLEDs have been commercially applied in some small devices, such as mobile phones, handheld computers, digital cameras, and streetlights. OFETs and OPVs have made great progress in practical application and are moving towards industrialization. One of the important ways to improve the properties of organic semiconductor devices is to develop new organic molecular materials. Organic molecular materials are a class of organic optoelectronic materials containing π-electronic structures and possessing optical, electrical, and magnetic properties, also known as organic semiconductor materials. Compared with inorganic materials, organic semiconductor materials have the advantages of easy molecular structure control, simple preparation process, low cost, and easy large-area fabrication of organic flexible circuits. In recent decades, the research and development of organic molecular materials has attracted widespread attention, thereby promoting the continuous improvement of the properties of organic semiconductor devices. Among them, fused-ring thiophene / selenophene compounds are an important class of conjugated molecular materials with very wide applications in the field of organic semiconductor devices. For example, 2,7-dioctyl[1]benzothiophene[3,2- b Benzothiophene blended with polystyrene as the semiconductor layer in a field-effect transistor achieves a mobility of up to 43 cm⁻¹. 2 V -1 s -1 . [See Y. Yuan, G. Giri, AL Ayzner, AP Zoombelt, SCBMannsfeld, J. Chen, D. Nordlund, MF Toney, J. Huang, Z. Bao, Nature Communications 2014, 5 , 3005. ] In addition, based on symmetrical 3,8-dihexyldiphenyl[ d , d ′]thiophene[3,2- b ;4,5- b The hole mobility of dithiophene-based OFETs devices can reach up to 18.9 cm⁻¹. 2 V -1 s -1. [See P. He, Z. Tu, G. Zhao, Y. Zhen, H. Geng, Y. Yi, Z. Wang, H. Zhang, C. Xu, J. Liu, X. Lu, X. Fu, Q. Zhao, X. Zhang, D. Ji, L. Jiang, H. Dong, W. Hu, Advanced Materials 2015, 27 [825-830.] Five common methods for synthesizing symmetrical fused-ring dibenzotrithiophene small molecule materials via cyclization reactions are as follows:

[0003] (1) Method 1: Intramolecular CS coupling cyclization reaction catalyzed by palladium

[0004]

[0005] This method requires expensive palladium catalysts and phosphine ligands, has a complex synthesis, moderate overall yield, and is sensitive to air, thus limiting its practical application. [See P. Oechsle, J. Paradies, Organic Letters 2014, 16 ,4086-4089.]

[0006] (2) Method 2: Intramolecular CS coupling cyclization reaction oxidized by strong oxidizing agent

[0007]

[0008] This method suffers from difficulties in substrate acquisition, requires the use of a strong oxidizing agent such as hydrogen peroxide, and is prone to explosion, thus limiting its practical value. [See FN Bilheri, AL Stein, G. Zeni, Advanced Synthesis & Catalysis 2015, 357 , 1221-1228.

[0009] (3) Method 3: Intramolecular CS coupling cyclization reaction catalyzed by electrochemical catalysis

[0010]

[0011] This method is difficult to obtain substrates and is complex to operate, thus its practical value is low. [See K. Mitsudo, R. Matsuo, T. Yonezawa, H. Inoue, H. Mandai, S. Suga, Angewandte Chemie- International Edition 2020, 59 , 7803-7807.]

[0012] (4) Method 4: Intramolecular CS coupling cyclization reaction catalyzed by PdCl2 / DMSO

[0013] This method requires an expensive palladium catalyst, has difficult substrate acquisition, low yield, and is sensitive to air, thus limiting its practical value. [See T. Zhang, G. Deng, H. Li, B. Liu, Q. Tan, B. Xu, Organic Letters 2018, 20 , 5439-5443.]

[0014] (5) Method 5: Lewis acid-mediated intermolecular CS coupling cyclization reaction

[0015] This method requires a transition metal catalyst, and the substrate is expensive, thus limiting its practical applicability. [See SMRafiq, R. Sivasakthikumaran, AK Mohanakrishnan, Organic Letters 2014, 16 ,2720-2723.

[0016] Asymmetric dibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b There is only one reported example of thiophene synthesis: an intramolecular CS coupling cyclization reaction via a dianionic intermediate.

[0017]

[0018] This method involves complex substrate synthesis and requires the use of highly flammable tert-butyllithium, which is extremely dangerous, thus limiting its practical value. This is a suggested synthetic route; no actual synthesis has been performed, and no yield or characterization data have been reported. [See Yiliang Wu, Oakville (CA); Ping Liu, Mississauga (CA); Anthony James Wigglesworth, Oakville (CA). Non-Symmetrical Dibenzodithienothiophene Compounds[P]. US8372312 B1, Feb. 12, 2013.]

[0019] In summary, existing techniques for synthesizing symmetrical dibenzotrithiophene small molecule materials suffer from the following problems: 1) complex substrate synthesis, which is time-consuming and labor-intensive; 2) the need for expensive palladium catalysts, resulting in high costs and sensitivity to air, making operation inconvenient; and 3) the need for strong oxidants such as hydrogen peroxide, which is prone to explosion. Therefore, these techniques have limited practical value. Furthermore, the molecule has poor solubility, making large-scale production difficult. Currently, only one patent reports the synthesis of asymmetric dibenzotrithiophene, which requires the use of the superbase tert-butyllithium, which is highly flammable. However, we have developed a metal-free, highly efficient method for synthesizing asymmetric dibenzotrithiophene. Summary of the Invention

[0020] To address the problems existing in the prior art, this invention provides a novel method for preparing asymmetric diaryltrithiophene / selenophene small molecule materials and their applications.

[0021] This invention is achieved as follows: the preparation method of the asymmetric diaryltrithiophene / selenophene small molecule material includes the following steps:

[0022] Step 1: Using 1-chloro-2-iodobenzene, 1-chloro-2-bromobenzene or 1-bromo-2-iodobenzene and its derivatives and trimethylethynylsilane as raw materials, the TMS (trimethylsilane) is removed by coupling reaction with scallion, and potassium fluoride is used as a base to obtain key intermediate 3;

[0023] Step 2: Using S8 or Se as the sulfur source or selenium source and potassium carbonate as the base, a series of fused-ring thiophene / selenophene small molecule materials were synthesized through a cascade cyclization reaction.

[0024] Furthermore, the synthetic route for preparing the asymmetric diaryltrithiophene / selenophene small molecule material is as follows:

[0025]

[0026] The Ar is selected from any one of aryl, heteroaryl, aryl containing substituents, and heteroaryl containing substituents; the substituent R is one or more of hydrogen, halogen, C1-C30 alkyl, C1-C30 alkoxy, trifluoromethyl, trifluoromethoxy, hydroxyl, aryl, acyl, ester, nitro, amino, and (C1-C30 alkyl)amine, and the position of the substituent is any position on the Ar ring; the base is any one of potassium carbonate, potassium acetate, cesium carbonate, cesium acetate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, dipotassium hydrogen phosphate, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, and 4-dimethylaminopyridine.

[0027] The amount of bis(triphenylphosphine) palladium dichloride catalyst and cuprous iodide catalyst added is generally 0.02-0.20 equivalents of the initial amount of reactants.

[0028] The coupling reaction conditions for sage were as follows: Compound 1 (1 equivalent) and Compound 2 (1.5 equivalent) were added to a mixed solvent of triethylamine and tetrahydrofuran (volume ratio 1:1), nitrogen was purged to remove oxygen, and 0.03 equivalents of bis(triphenylphosphine)-palladium dichloride catalyst and 0.06 equivalents of cuprous iodide catalyst were added to the system. The reaction was carried out at 30°C. o C reaction takes 5 hours.

[0029] The metal-free cascade cyclization reaction conditions are as follows: compound 3 (1 equivalent), S8 (0.5 equivalent) or Se (4 equivalent), and base (1 equivalent) are added to the solvent N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, and the reaction is carried out at 145°C for 48 hours.

[0030] Another objective of this invention is to provide a method for preparing asymmetric diaryltrithiophene / selenophene small molecule materials, the molecular structure of which is as follows:

[0031]

[0032] Another object of the present invention is to provide an organic semiconductor device made from the aforementioned asymmetric diaryltrithiophene / selenophene small molecule material.

[0033] Another object of the present invention is to provide a mobile phone manufactured from the organic semiconductor device.

[0034] Another object of the present invention is to provide a handheld computer made of the organic semiconductor device.

[0035] The advantages and positive effects of this invention are as follows: the substrate of this invention is simple to synthesize, the raw materials are inexpensive and readily available; no metals are involved; it can be carried out under air conditions; the reaction efficiency is high, and three rings can be fused simultaneously in one step; the yield is moderate, and the yield can still reach 58% even with a large-scale reaction (10 mmol). Therefore, this method is suitable for industrial production. Attached Figure Description

[0036] Figure 1 This is a flowchart of the preparation method of the asymmetric diaryltrithiophene / selenophene small molecule material provided in the embodiments of the present invention.

[0037] Figure 2 This is a schematic diagram of the cyclic voltammetry curve of DBDTT (solvent dichloromethane, highest occupied orbital energy level: -5.69 eV) provided in the embodiments of the present invention.

[0038] Figure 3This is a schematic diagram of the cyclic voltammetry curve of D-C8-DBDTT (solvent dichloromethane, highest occupied orbital energy level: -5.57 eV) provided in an embodiment of the present invention.

[0039] Figure 4 This is a schematic diagram of the cyclic voltammetry curve of C8-DBDTT (solvent dichloromethane, highest occupied orbital energy level: -5.61 eV) provided in the embodiments of the present invention. Detailed Implementation

[0040] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0041] The application principle of the present invention will be described in detail below with reference to the accompanying drawings.

[0042] The molecular structure of the asymmetric diaryltrithiophene / selenophene small molecule material provided in this invention embodiment is as follows:

[0043] ;

[0044] Y = S, Se.

[0045] like Figure 1 As shown, the preparation method of the asymmetric diaryltrithiophene / selenophene small molecule material provided in this embodiment of the invention includes the following steps:

[0046] S101: Using 1-chloro-2-iodobenzene, 1-chloro-2-bromobenzene or 1-bromo-2-iodobenzene and its derivatives and trimethylethynylsilane as raw materials, after a sorghum coupling reaction, potassium fluoride is used as a base to remove TMS (trimethylsilyl) to obtain key intermediate 3;

[0047] S102: Using S8 or Se as the sulfur source or selenium source and potassium carbonate as the base, a series of fused-ring thiophene / selenophene small molecule materials were synthesized through a cascade cyclization reaction.

[0048] The synthetic route for preparing the asymmetric diaryltrithiophene / selenophene small molecule material provided in this invention is as follows:

[0049]

[0050] Ar is selected from any one of aryl, heteroaryl, aryl containing a substituent, and heteroaryl containing a substituent; the substituent R is one or more of hydrogen, halogen, C1-C30 alkyl, C1-C30 alkoxy, trifluoromethyl, trifluoromethoxy, hydroxyl, aryl, acyl, ester, nitro, amino, and (C1-C30 alkyl)amine, and the position of the substituent is any position on the Ar ring; the base is any one of potassium carbonate, potassium acetate, cesium carbonate, cesium acetate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, dipotassium hydrogen phosphate, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, and 4-dimethylaminopyridine.

[0051] In the above synthesis method, the amount of bis(triphenylphosphine) palladium dichloride catalyst and cuprous iodide catalyst added is generally 0.02-0.20 equivalents of the initial amount of reactants.

[0052] The coupling reaction conditions for sage were as follows: Compound 1 (1 equivalent) and Compound 2 (1.5 equivalent) were added to a mixed solvent of triethylamine and tetrahydrofuran (volume ratio 1:1), nitrogen was purged to remove oxygen, and 0.03 equivalents of bis(triphenylphosphine)-palladium dichloride catalyst and 0.06 equivalents of cuprous iodide catalyst were added to the system. The reaction was carried out at 30°C. o C reaction takes 5 hours.

[0053] The metal-free cascade cyclization reaction conditions are as follows: compound 3 (1 equivalent), S8 (0.5 equivalent) or Se (4 equivalent), and base (1 equivalent) are added to the solvent N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone, at 145 °C. o C reaction takes 48 hours.

[0054] In the above synthesis method, the amount of bis(triphenylphosphine) palladium dichloride catalyst and cuprous iodide catalyst added is generally 0.02-0.20 equivalents of the initial amount of reactants.

[0055] The coupling reaction conditions for sage were as follows: Compound 1 (1 equivalent) and Compound 2 (1.5 equivalent) were added to a mixed solvent of triethylamine and tetrahydrofuran (volume ratio 1:1), nitrogen was purged to remove oxygen, and 0.03 equivalents of bis(triphenylphosphine)-palladium dichloride catalyst and 0.06 equivalents of cuprous iodide catalyst were added to the system. The reaction was carried out at 30°C. o C reaction takes 5 hours.

[0056] Compound 3 (1 equivalent), S8 (0.5 equivalent) or Se (4 equivalent), and a base (1 equivalent) are added to the solvent N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone, at 145 o C reaction takes 48 hours.

[0057] Metal-free cascade cyclization reactions are used to synthesize thiophene / selenophene compounds, including fused-ring thiophene-thiophene, fused-ring selenophene-selenophene, fused-ring pyridothiophene, fused-ring pyridoselenene, fused-ring pyrrolothiophene, fused-ring pyrroloselenene and their derivatives (alkyl chain substitution, aromatic compound substitution, halogen substitution and trifluoromethyl, trifluoromethoxy and other substituent groups);

[0058] The sulfur source is elemental sulfur, and the selenium source is elemental selenium.

[0059] The bases include potassium carbonate, potassium acetate, cesium carbonate, cesium acetate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, dipotassium hydrogen phosphate, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, 4-dimethylaminopyridine, etc., with potassium carbonate being the preferred choice.

[0060] The solvent for the metal-free cascade cyclization reaction is N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, with N-methylpyrrolidone being preferred;

[0061] The temperature for metal-free cascade cyclization reactions is generally 145 °C.

[0062] The time for a metal-free cascade cyclization reaction is generally 48 h;

[0063] The catalysts for the coupling reaction of sage are palladium dichloride and cuprous iodide, and the solvents are triethylamine and tetrahydrofuran (volume ratio 1:1).

[0064] Pd and Cu catalyze selective coupling reaction of sorghum;

[0065] Fabrication and application of organic field-effect transistors based on fused-ring thiophene / selenophene small molecule materials in this patent.

[0066] The application principle of the present invention will be further described below with reference to specific embodiments.

[0067] Example 1: Dibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0068]

[0069] 1) Accurately weigh 1-chloro-2-ethynylbenzene (136 mg, 1 mmol), elemental sulfur (128 mg, 0.5 mmol), and potassium carbonate (138 mg, 1 mmol), and add them sequentially to a 25 mL Schlenk flask. Add N-methylpyrrolidone (4 mL), and react in a 145 °C heating element for 48 hours. After the reaction is complete, remove the solvent under reduced pressure, separate using a silica gel column with petroleum ether as the eluent, and obtain the target product 4a in 62% yield. 1 H NMR (400 MHz, deuterated chloroform): d 8.03-8.01 (m,1H), 7.95-7.93 (m, 1H), 7.90-7.85 (m, 2H), 7.55-7.51 (m, 1H), 7.48-7.44 (m,1H), 7.43-7.36 (m, 2H). 13 C NMR (101 MHz, deuterated chloroform): d 143.44, 141.49, 140.12, 135.89, 133.70, 132.98, 131.65, 129.85, 125.11, 124.52, 124.40, 124.23, 123.33, 121.71, 120.50. High-resolution mass spectrometry (ESI): m / z for C 16 H8S3[M] + Calculated value: 295.9788; Measured value: 295.9786.

[0070] Example 2 2,7-Dimethyldibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0071]

[0072] 1) Accurately weigh 2-chloro-1-iodo-4-methylbenzene (700 µL, 1.27 g, 5 mmol) and add it to a 250 mL Schlenk flask. Vacuum the flask and purge it with nitrogen three times. Under nitrogen protection, add triethylamine and tetrahydrofuran (volume ratio 1:1). Bubble nitrogen to remove oxygen for 15 min. Under nitrogen protection, add trimethylethynylsilane (1.42 mL, 983 mg, 10 mmol), palladium dichloride bis(triphenylphosphine) (71 mg, 0.1 mmol), and cuprous iodide (39 mg, 0.2 mmol). Place the flask in a 30 °C heating module and react for 5 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column chromatography with petroleum ether as the eluent to give 2-chloro-4-methylphenylethynyltrimethylsilane. Using this as a substrate, potassium fluoride (390 mg, 5 mmol) and methanol (20 mL) were added, and the mixture was reacted in a heating element at 30 °C for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column chromatography with petroleum ether as the eluent to give 2-chloro-1-ethynyl-4-methylbenzene in 77% yield. 1 H NMR (400 MHz, deuterated chloroform): d 7.41 (d, J = 8.0 Hz, 1H), 7.23 (s, 1H), 7.02 (m, 1H), 3.32 (s, 1H), 2.24 (s, 3H). 13 C NMR (101 MHz, deuterated chloroform): d 140.71, 135.98, 133.80, 129.94, 127.50, 119.02, 81.66, 80.48, 21.36. High-resolution mass spectrometry (ESI mode): m / z for C9H7Cl [M+H] + Calculated value: 151.0309; Measured value: 151.0306.

[0073] 2) The product obtained in step 1) (136 µL, 151 mg, 1 mmol), elemental sulfur (128 mg, 0.5 mmol), and potassium carbonate (138 mg, 1 mmol) were sequentially added to a 25 mL Schlenk flask, followed by 4 mL of N,N-dimethylformamide. The mixture was then placed in a heating element at 145 °C and reacted for 48 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to obtain the target product 4b in 52% yield. 1 H NMR (400 MHz, deuterated tetrachloroethane): d 7.84 (d, J= 8.0 Hz, 1H), 7.72 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.67 (s, 1H), 7.31 (dd, J = 8.1, 1.5 Hz, 1H), 7.26 (dd, J = 8.1, 1.5 Hz, 1H), 2.50 (s, 3H), 2.49 (s, 3H). 13 C NMR (101 MHz, deuterated tetrachloroethane): d 143.73, 141.79, 138.62, 135.83, 134.85, 134.74, 133.62, 130.71, 129.29, 128.95, 126.84, 126.72, 124.24, 123.50, 121.36, 120.24, 21.88. High-resolution mass spectrometry (ESI mode): m / z for C 18 H 12 S3[M] + Calculated value: 324.0096, measured value: 324.0084.

[0074] Example 3 2,7-Di(trifluoromethoxy)dibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0075]

[0076] 1) Accurately weigh 2-chloro-1-iodo-4-trifluoromethoxybenzene (820 µL, 1.613 g, 5 mmol) and add it to a 250 mL Schlenk flask. Vacuum the flask and purge it with nitrogen three times. Under nitrogen protection, add triethylamine and tetrahydrofuran (volume ratio 1:1). Bubble nitrogen to remove oxygen for 15 min. Under nitrogen protection, add trimethylethynylsilane (1.42 mL, 983 mg, 10 mmol), palladium dichloride bis(triphenylphosphine) (106 mg, 0.15 mmol), and cuprous iodide (58 mg, 0.3 mmol). Place the flask in a 30 °C heating module and react for 5 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-4-trifluoromethoxy-phenylethynyltrimethylsilane. Using this as a substrate, potassium fluoride (390 mg, 5 mmol) and methanol (20 mL) were added, and the mixture was reacted in a 30 °C heating module for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-1-ethynyl-4-trifluoromethoxybenzene in 74% yield. 1 HNMR (400 MHz, deuterated chloroform): d 7.55 (dd, J = 8.6, 1.0 Hz, 1H), 7.29 (s, 1H), 7.11-7.08 (m, 1H), 3.39 (s, 1H). 13 C NMR (101 MHz, deuterated chloroform): d 149.27, 137.50,134.98, 122.00, 120.98, 120.30 (q, 1 J C-F = 260.18Hz), 119.12, 83.42, 79.06. High-resolution mass spectrometry (ESI mode): m / z for C9H5ClF3O [M+H] + Calculated value: 220.9976; Measured value: 220.9968.

[0077] 2) The product obtained in step 1) (221 mg, 1 mmol), elemental sulfur (128 mg, 0.5 mmol), and potassium carbonate (138 mg, 1 mmol) were added sequentially to a 25 mL Schlenk flask, followed by 4 mL of N-methylpyrrolidone. The mixture was then placed in a heating element at 145 °C for 48 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to obtain the target product 4c in 46% yield. 1H NMR (400 MHz, deuterated chloroform): d 7.96 (d, J = 8.6Hz, 1H), 7.84 (d, J = 8.5 Hz, 1H), 7.80 (s, 1H), 7.76 (s, 1H), 7.42 (d, J = 8.6Hz, 1H), 7.35 (d, J = 8.5 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): d 146.46, 146.27,144.16, 142.29, 141.24, 135.60, 132.90, 131.57, 130.42, 130.11, 122.23,121.15, 120.72 (q, 1 J C-F = 258.76 Hz), 119.16-118.96 (m), 116.74, 115.96. High-resolution mass spectrometry (ESI mode): m / z for C 18 H6F6O2S3[M] + Calculated value: 463.9429; Measured value: 463.9406.

[0078] Example 4 2,7-Difluorodibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0079]

[0080] 1) Accurately weigh 2-chloro-4-fluoro-1-iodobenzene (639µL, 1.282 g, 5 mmol) and add it to a 250 mL Schlenk flask. Vacuum the flask and purge it with nitrogen three times. Under nitrogen protection, add triethylamine and tetrahydrofuran (volume ratio 1:1). Bubble nitrogen to remove oxygen for 15 min. Under nitrogen protection, add trimethylethynylsilane (1.42 mL, 983 mg, 10 mmol), palladium dichloride bis(triphenylphosphine) (106 mg, 0.15 mmol), and cuprous iodide (58 mg, 0.3 mmol). Place the flask in a 30 °C heating module and react for 5 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-4-fluorophenylethynyltrimethylsilane. Using this as a substrate, potassium fluoride (390 mg, 5 mmol) and methanol (20 mL) were added, and the mixture was reacted in a 30 °C heating module for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-1-ethynyl-4-fluorobenzene in 64% yield. 1 H NMR (400 MHz, deuterated chloroform): d 7.51 (dd, J = 8.6, 5.9 Hz, 1H), 7.16 (dd, J = 8.5, 2.6 Hz, 1H), 6.96 (td, J = 8.3,2.6 Hz, 1H), 3.34 (s, 1H). 13 C NMR (101 MHz, deuterated chloroform): d 162.39 (d, 1 J C-F = 252.2Hz), 137.58 (d, 3 J C-F = 10.5 Hz), 135.25 (d, 3 J C-F = 9.1 Hz), 118.47 (d, 4 J C-F = 3.9Hz), 117.14 (d, 2 J C-F = 25.1 Hz), 114.34 (d, 2 J C-F = 21.7 Hz), 82.28, 79.37. High-resolution mass spectrometry (ESI mode): m / z for C8H5ClF [M+H] + Calculated value: 155.0058; Measured value: 155.0054.

[0081] 2) The product obtained in step 1) (62 µL, 77.5 mg, 0.5 mmol), elemental sulfur (64 mg, 0.25 mmol), and potassium carbonate (69 mg, 0.5 mmol) were sequentially added to a 25 mL Schlenk flask, followed by 2 mL of N,N-dimethylformamide. The mixture was then placed in a heating element at 145 °C and reacted for 48 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to obtain the target product 4d, with a yield of 16%. 1 H NMR (400 MHz, deuterated tetrachloroethane): d 7.91 (dd, J = 8.7, 5.1 Hz, 1H), 7.81 (dd, J = 8.7, 5.1 Hz, 1H), 7.65 (d, J = 8.7Hz, 1H), 7.61 (d, J = 8.7 Hz, 1H), 7.32-7.20 (m, 2H). 13 C NMR (101 MHz, deuterated tetrachloroethane): d 160.58 (q, 1 J C-F = 247.25 Hz), 160.45 (q, 1 J C-F = 246.44 Hz), 144.62 (d, 3 J C-F =9.09 Hz), 142.73(d, 3 J C-F = 10.1 Hz),139.25, 135.85, 133.22, 129.67, 129.39 (d, 4 J C-F = 3.13 Hz), 128.26 (d, 4 J C-F = 4.04 Hz), 122.47 (q, 3 J C-F= 10.1 Hz), 122.43 (q, 3 J C-F = 8.08 Hz), 110.69 (d, 2 J C-F = 25.86 Hz), 110.09 (d, 2 J C-F = 26.26 Hz). High-resolution mass spectrometry (ESI mode): m / z for C 16 H6F2S3[M] + Calculated value: 331.9594, measured value: 331.9585.

[0082] Example 5 2,7-Di(trifluoromethyl)dibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0083]

[0084] 1) Accurately weigh 2-chloro-1-iodo-4-trifluoromethylbenzene (789µL, 1.54 g, 5 mmol) and add it to a 250 mL Schlenk flask. Vacuum the flask and purge it with nitrogen three times. Under nitrogen protection, add triethylamine and tetrahydrofuran (volume ratio 1:1). Bubble nitrogen to remove oxygen for 15 min. Under nitrogen protection, add trimethylethynylsilane (1.42 mL, 983 mg, 10 mmol), palladium dichloride bis(triphenylphosphine) (106 mg, 0.15 mmol), and cuprous iodide (58 mg, 0.3 mmol). Place the flask in a 30°C heating module and react for 5 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-4-trifluoromethylphenylethynyltrimethylsilane. Using this as a substrate, potassium fluoride (390 mg, 5 mmol) and methanol (20 mL) were added, and the mixture was reacted in a 30 °C heating module for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-1-ethynyl-4-trifluorotoluene in 46% yield. 1 H NMR (400MHz, deuterated chloroform): d 7.67 (s, 1H), 7.63 (d, J = 8.1 Hz, 1H), 7.48 (d, J = 8.1 Hz, 1H), 3.50 (s, 1H). 13C NMR (101 MHz, deuterated chloroform): d 137.02, 134.41, 131.86 (q, 2 J C-F =33.33), 126.45 (q, 3 J C-F = 3.94), 125.87, 123.41 (q, 3 J C-F = 4.04), 123.08 (q, 1 J C-F =273.71), 85.05, 79.12. High-resolution mass spectrometry (ESI mode): m / z for C9H4F3Cl [M] + Calculated value: 203.9948; Measured value: 203.9940.

[0085] 2) The product obtained in step 1) (205 mg, 1 mmol), elemental sulfur (128 mg, 0.5 mmol), and potassium carbonate (138 mg, 1 mmol) were added sequentially to a 25 mL Schlenk flask, followed by 4 mL of N-methylpyrrolidone. The mixture was then placed in a heating element at 145 °C for 48 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to obtain the target product 4e in 45% yield. 1 H NMR (400 MHz, deuterated chloroform): d 8.23 (s, 1H),8.18 (s, 1H), 8.09 (d, J = 8.3 Hz, 1H), 7.95 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.3Hz, 1H), 7.71 (d, J = 8.4 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): d 144.26, 143.29,141.33, 135.78, 135.10, 133.72, 132.98, 132.11, 127.12 (q, 2 J C-F = 33.13),126.94 (q, 2 JC-F = 32.62,),124.33 (q, 1 J C-F = 273.81), 122.25,121.84, 121.63 (q, 3 J C-F = 4.24), 120.75, 120.69 (q, 3 J C-F = 3.74). High-resolution mass spectrometry (ESI mode): m / z for C 18 H6F6S3[M] + Calculated value: 431.9530; Measured value: 431.9513.

[0086] Example 6 4,9-Dimethyldibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0087]

[0088] 1) Accurately weigh 420 µL (757.4 mg, 3 mmol) of 1-chloro-2-iodo-3-toluene into a 250 mL Schlenk flask. Evacuate the flask three times with nitrogen. Under nitrogen protection, add triethylamine and tetrahydrofuran (1:1 v / v). Bubble nitrogen for 15 min to remove oxygen. Then, under nitrogen protection, add trimethylethynylsilane (848 µL, 589 mg, 6 mmol), palladium dichloride (64 mg, 0.09 mmol), and cuprous iodide (35 mg, 0.18 mmol). React in a 30 °C heating element for 5 hours. After the reaction, remove the solvent under reduced pressure and separate using a silica gel column with petroleum ether as the eluent to obtain 2-chloro-6-tolueneethynyltrimethylsilane. Use this as a substrate, add potassium fluoride (234 mg, 3 mmol) and methanol (20 mL), and react in a 35 °C heating element for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 1-chloro-2-ethynyl-3-toluene in 70% yield. 1 H NMR (400 MHz, deuterated chloroform): d 7.24 (d, J = 8.7 Hz, 1H), 7.16 (t, J = 7.7 Hz, 1H), 7.11 (d, J= 7.6 Hz, 1H), 3.60 (s, 1H), 2.47 (s, 3H). 13 C NMR (101 MHz, deuterated chloroform): d 143.30, 136.53, 129.17, 127.71, 126.60, 122.00, 86.66, 79.14, 21.39. High-resolution mass spectrometry (ESI mode): m / z for C9H8Cl [M+H] + Calculated value: 151.0309; Measured value: 151.0304.

[0089] 2) The product obtained in step 1) (136 µL, 1 mmol), elemental sulfur (128 mg, 0.5 mmol), and potassium carbonate (138 mg, 1 mmol) were added sequentially to a 25 mL Schlenk flask, followed by 4 mL of N-methylpyrrolidone. The mixture was then placed in a heating element at 145 °C for 48 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give the target product 4f in 18% yield. 1 H NMR (400 MHz, deuterated chloroform): d 7.69 (t, J = 8.4 Hz, 2H),7.28-7.19 (m, 4H), 3.20 (s, 3H), 2.76 (s, 3H). 13 C NMR (101 MHz, deuterated chloroform): d 143.59, 141.12, 140.82, 135.91, 133.68, 132.97, 132.39, 131.84, 131.02, 130.15, 126.71, 125.87, 124.80, 124.56, 121.14, 120.87, 23.11, 20.55. High-resolution mass spectrometry (ESI mode): m / z for C 18 H 12 S3[M] + Calculated value: 324.0096; Measured value: 324.0087.

[0090] Example 7 3,8-Di(trifluoromethyl)dibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0091]

[0092] 1) Accurately weigh 1-chloro-2-iodo-4-trifluoromethylbenzene (785 µL, 1.533 g, 5 mmol) and add it to a 250 mL Schlenk flask. Vacuum the flask and purge it with nitrogen three times. Under nitrogen protection, add triethylamine and tetrahydrofuran (volume ratio 1:1). Bubble nitrogen to remove oxygen for 15 min. Under nitrogen protection, add trimethylethynylsilane (1.42 mL, 983 mg, 10 mmol), palladium dichloride bis(triphenylphosphine) (106 mg, 0.15 mmol), and cuprous iodide (58 mg, 0.3 mmol). Place the flask in a 30 °C heating module and react for 5 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 2-chloro-5-trifluoromethylphenylethynyltrimethylsilane. Using this as a substrate, potassium fluoride (390 mg, 5 mmol) and methanol (20 mL) were added, and the mixture was reacted in a 30 °C heating module for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 1-chloro-2-ethynyl-4-trifluorotoluene in 53% yield. 1 H NMR (400MHz, deuterated chloroform): d 7.79 (s, 1H), 7.79 (s, 2H), 3.47 (s, 1H). 13 C NMR (101 MHz, deuterated chloroform): d 139.89, 130.59 (q, 3 J C-F = 4.04), 129.87, 129.17 (q, 2 J C-F = 33.33), 125.95(q, 3 J C-F = 3.84), 124.01, 123.42 (q, 1 J C-F = 273.81), 102.52, 99.75. High-resolution mass spectrometry (ESI mode): m / z for C9H5ClF3[M+H] + Calculated value: 205.0026; Measured value: 205.0021.

[0093] 2) The product obtained in step 1) (76 µL, 102.3 mg, 0.5 mmol), elemental sulfur (64 mg, 0.25 mmol), and potassium carbonate (69 mg, 0.5 mmol) were sequentially added to a 25 mL Schlenk flask, followed by 2 mL of N-methylpyrrolidone. The mixture was then placed in a heating element at 145 °C and reacted for 48 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to obtain 4 g of the target product, with a yield of 35%. 1 H NMR (400 MHz, deuterated tetrachloroethane): d 8.18 (s, 1H), 8.12 (s, 1H), 8.06 (d, J = 8.6 Hz, 1H), 8.02 (d, J = 8.4 Hz, 1H), 7.66 (d, J = 8.7 Hz, 1H), 7.62 (d, J = 8.3 Hz, 1H). 13 C NMR (101 MHz, deuterated tetrachloroethane): d 146.80, 144.81, 143.01, 136.27, 133.23, 132.62, 131.26, 131.19, 128.04(q, 2 J C-F = 32.93), 124.88, 124.00, 124.51 (q, 1 J C-F = 274.22), 121.24, 121.13,118.60 (q, 3 J C-F = 4.89), 117.66 (q, 3 J C-F = 4.44). High-resolution mass spectrometry (ESI mode): m / z forC 18 H6F6S3[M] + Calculated value: 431.9530; Measured value: 431.9510.

[0094] Example 8 3,8-Dichlorodibenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0095]

[0096] 1) Accurately weigh 1,4-dichloro-2-iodobenzene (1.37 g, 5 mmol) and add it to a 250 mL Schlenk flask. Evacuate the flask three times with nitrogen. Under nitrogen protection, add triethylamine and tetrahydrofuran (1:1 volume ratio). Bubble nitrogen for 15 min to remove oxygen. Then, under nitrogen protection, add trimethylethynylsilane (1.42 mL, 983 mg, 10 mmol), palladium dichloride bis(triphenylphosphine) (106 mg, 0.15 mmol), and cuprous iodide (58 mg, 0.3 mmol). React in a 30 °C heating element for 5 hours. After the reaction, remove the solvent under reduced pressure and separate using a silica gel column with petroleum ether as the eluent to obtain 2,5-dichlorophenylethynyltrimethylsilane. Use this as a substrate, add potassium fluoride (390 mg, 5 mmol) and methanol (20 mL), and react in a 30 °C heating element for 7 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column with petroleum ether as the eluent to give 1-chloro-2-ethynyl-4-trifluorotoluene in 81% yield. 1 1H NMR (400 MHz, deuterated dimethyl sulfoxide): d 7.70(d, J = 2.4 Hz, 1H), 7.57 (d, J = 8.7 Hz, 1H), 7.49 (dd, J = 8.7, 2.5 Hz, 1H), 4.72(s, 1H). 13 C NMR (101 MHz, deuterated dimethyl sulfoxide): d 134.33, 133.66, 132.33, 131.49, 131.16, 123.62, 88.26, 79.33. High-resolution mass spectrometry (ESI mode): m / z for C8H4Cl2[M] + Calculated value: 169.9684; Measured value: 169.9680.

[0097] 2) The product obtained in step 1) (85.5 mg, 0.5 mmol), elemental sulfur (64 mg, 0.25 mmol), and potassium carbonate (69 mg, 0.5 mmol) were added sequentially to a 25 mL Schlenk flask, followed by 2 mL of N-methylpyrrolidone. The mixture was then placed in a heating element at 145 °C and reacted for 48 hours. After the reaction was complete, the N-methylpyrrolidone was washed off with methanol, and the solution was then sublimated to give 4 g of the target product, with a yield of 17%. 1 H NMR (400 MHz, deuterated chloroform): d 7.96 (d, J = 2.1 Hz, 1H), 7.85(d, J = 8.4 Hz, 1H), 7.85 (d, J = 2.0 Hz, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.40 (dd, J = 8.6, 2.0 Hz, 1H), 7.36 (dd, J = 8.8, 1.6 Hz, 1H). High-resolution mass spectrometry (ESI mode): m / z forC 16 H6Cl2S3[M] + Calculated value: 363.9003, measured value: 363.8980.

[0098] Example 9 2-Octylbenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0099]

[0100] 1) Accurately weigh octanoyl chloride (712µL, 684.6mg, 2.1 mmol) and aluminum chloride (559mg, 2.1 mmol) into a 250 mL Schlenk flask. Vacuum the flask, purge with nitrogen three times, and add anhydrous dichloromethane (40 mL) under nitrogen protection. React in a 30 °C heating element for 2 hours. Then, under nitrogen protection, add dibenzo[…]. d,d' Dithiophene[2,3-] b :2',3'- b Thiophene (592 mg, 2 mmol) was reacted in a 60 °C (reflux) heating module for 12 hours. After the reaction, the solvent was removed under reduced pressure, and the mixture was separated by chromatography using dichloromethane and ethanol to obtain 2-(n-octanoyl)benzo[ d,d' Dithiophene[2,3-] b :2',3'- b Thiophene (673.5 mg, 1.59 mmol), yield 80%. 1 H NMR (400 MHz, deuterated chloroform): d 8.55 (s, 1H), 8.05 (d, J = 8.4 Hz, 1H), 8.02 (d, J = 7.8 Hz, 1H), 7.88(d,J = 7.2 Hz, 2H), 7.54 (t, J = 7.5 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H), 3.05 (t, J =7.4 Hz, 2H), 1.79 (p, J = 7.4 Hz, 2H), 1.47-1.28 (m, 8H), 0.96-0.78 (m, 3H). 13 CNMR (101 MHz, deuterated chloroform): d 199.46, 143.48, 142.13, 141.54, 136.10, 135.45, 133.76, 133.26, 133.13, 131.49, 125.28, 125.06, 124.81, 124.77, 123.35, 121.73, 120.13, 38.84, 31.79, 29.47, 29.22, 24.69, 22.68, 14.09. High-resolution mass spectrometry (ESI mode): m / z for C 24 H 23 OS3[M+H] + Calculated value: 423.0905; Measured value: 423.0902.

[0101] 2) The product obtained in step 1) (634 mg, 1.5 mmol), lithium aluminum hydride (228 mg, 6 mmol), and aluminum chloride (798 mg, 6 mmol) were added sequentially to a 250 mL Schlenk flask. Anhydrous diethyl ether and anhydrous dichloromethane (volume ratio 1:2) were added, and the mixture was placed in a 25 °C heating element for 12 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column chromatography with petroleum ether as the eluent to obtain the target product 4i (574 mg, 1.40 mmol), with a yield of 94%. 1 HNMR (400 MHz, deuterated chloroform): d 8.01 (dt, J = 7.9, 1.1 Hz, 1H), 7.87 (dt, J = 8.1, 0.9Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 7.73 (d, J = 1.5 Hz, 1H), 7.52 (ddd, J= 8.0,7.2, 1.1 Hz, 1H), 7.40 (ddd, J = 8.3, 7.2, 1.3 Hz, 1H), 7.28 (dd, J = 8.1, 1.5Hz, 1H), 2.75 (t, J = 8.0 Hz, 2H), 1.69 (p, J = 7.6 Hz, 2H), 1.33-1.26 (m, 10H), 0.91-0.85 (m, 3H). 13 C NMR (101 MHz, deuterated chloroform): d 143.44, 141.81, 139.75, 139.47, 135.86, 133.80, 131.69, 130.92, 129.07, 126.11, 125.04, 124.44, 123.52, 123.32, 121.73, 120.17, 36.20, 31.99, 31.89, 29.61, 29.43, 29.38, 22.78, 14.24. High-resolution mass spectrometry (ESI mode): m / z for C 24 H 24 S3[M] + Calculated value: 408.1035; Measured value: 408.1021.

[0102] Example 10 2,7-Dioctylbenzo[ d,d' Dithiophene[2,3-] b :2',3'- b Synthesis of thiophene

[0103]

[0104] 1) Accurately weigh octanoyl chloride (1.7 mL, 1.63 g, 10 mmol) and aluminum chloride (1.33 g, 10 mmol) into a 250 mL Schlenk flask. Vacuum the flask, purge with nitrogen three times, and add anhydrous dichloromethane (40 mL) under nitrogen protection. React in a 30 °C heating element for 2 hours. Then, under nitrogen protection, add dibenzo[…]. d,d' Dithiophene[2,3-] b :2',3'- b Thiophene (592 mg, 2 mmol) was reacted in a 60 °C (reflux) heating module for 12 hours. After the reaction, the solvent was removed under reduced pressure, and the mixture was separated by chromatography using dichloromethane and ethanol to obtain 2,8-bis(n-octanoyl)benzo[d, d' Dithiophene[2,3-] b :2',3'- b Thiophene (881.3 mg, 1.6 mmol), yield 80%. 1 H NMR (400 MHz, deuterated chloroform): d 8.54 (dd, J = 1.6, 0.6 Hz, 1H), 8.48 (dd, J = 1.5, 0.7 Hz, 1H), 8.10(dd, J = 8.3, 1.5 Hz, 1H), 8.04 (dd, J = 8.4, 1.5 Hz, 1H), 8.00 (dd, J = 8.3, 0.6Hz, 1H), 7.86 (dd, J = 8.4, 0.6 Hz, 1H), 3.05 (t, J = 7.4 Hz, 4H), 1.82-1.75 (m,4H), 1.44-1.29 (m, 16H), 0.89 (t, J = 7.2, 6H). 13 C NMR (101 MHz, deuterated chloroform): d 199.43, 199.34, 145.27, 143.32, 141.41, 135.66, 134.20, 133.23, 133.18, 133.05, 132.83, 125.02, 124.61, 123.56, 121.26, 120.16, 38.90, 38.86, 31.86, 29.50, 29.33, 24.56, 24.52, 22.77, 14.24. High-resolution mass spectrometry (ESI mode): m / z for C 32 H 37 O2S3[M+H] + Calculated value: 549.1950; Measured value: 549.1924.

[0105] 2) The product obtained in step 1) (824 mg, 1.5 mmol), lithium aluminum hydride (342 mg, 9 mmol), and aluminum chloride (1.2 g, 9 mmol) were added sequentially to a 25 mL Schlenk flask, along with anhydrous diethyl ether and anhydrous dichloromethane (volume ratio 1:2). The mixture was then placed in a heating element at 25 °C and reacted for 2 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated using a silica gel column chromatography with petroleum ether as the eluent to obtain the target product 4j (442 mg, 0.85 mmol), with a yield of 57%. 1 H NMR (400 MHz, deuterated chloroform): d 7.91 (d, J = 8.0 Hz, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.72 (s,1H), 7.67 (s, 1H), 7.33 (dd, J = 8.1, 1.5 Hz, 1H), 7.27 (dd, J = 8.1, 1.4 Hz,1H), 2.78-2.74 (m, 4H), 1.73-1.65 (m, 4H), 1.39-1.20 (m, 20H), 0.87 (t, J = 6.8Hz, 6H). 13 C NMR (101 MHz, deuterated chloroform): d 143.73, 141.80, 139.69, 139.62, 138.54, 135.73, 133.68, 131.00, 129.62, 129.03, 126.05, 125.95, 123.50, 122.72, 121.35, 120.12, 76.80, 36.19, 32.00, 31.89, 29.61, 29.44, 29.39, 22.79, 14.24. High-resolution mass spectrometry (ESI mode): m / z for C 32 H 40 S3[M] + Calculated value: 520.2287; Measured value: 520.2265.

[0106] Example 11 Measurement of the highest occupied molecular orbital of DBDTT using electrochemical cyclic voltammetry

[0107] The electrochemical properties of DBDTT, the product obtained in Example 1, were tested using an electrochemical workstation. Ferrocene was used as an internal standard, and the electrolyte was a 0.001 M solution of tetrabutylammonium hexafluorophosphate in dichloromethane. A standard three-electrode system was employed, with a platinum wire as the counter electrode and a silver chloride electrode as the reference electrode. The cyclic voltammetry curves were obtained as follows: Figure 2 As shown, the highest occupied molecular orbital energy level of DBDTT can be calculated to be -5.69 eV.

[0108] Example 12 Measurement of the highest occupied molecular orbital of D-C8-DBDTT using electrochemical cyclic voltammetry

[0109] The electrochemical properties of the product D-C8-DBDTT obtained in Example 1 were tested using an electrochemical workstation. Ferrocene was used as an internal standard, and the electrolyte was a 0.001 M solution of tetrabutylammonium hexafluorophosphate in dichloromethane. A standard three-electrode system was used for the tests, with a platinum wire as the counter electrode and a silver chloride electrode as the reference electrode. The cyclic voltammetry curves were obtained as follows: Figure 3 As shown, the highest occupied molecular orbital energy level of D-C8-DBDTT can be calculated to be -5.57 eV.

[0110] Example 13 Measurement of the highest occupied molecular orbital of C8-DBDTT using electrochemical cyclic voltammetry

[0111] The electrochemical properties of the product C8-DBDTT obtained in Example 1 were tested using an electrochemical workstation. Ferrocene was used as an internal standard, and the electrolyte was a 0.001 M solution of tetrabutylammonium hexafluorophosphate in dichloromethane. A standard three-electrode system was used for the tests, with a platinum wire as the counter electrode and a silver chloride electrode as the reference electrode. The cyclic voltammetry curves were obtained as follows: Figure 4 As shown, the highest occupied molecular orbital energy level of C8-DBDTT can be calculated to be -5.61 eV.

[0112] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing asymmetric diaryltrithiophene small molecule materials, characterized in that, The synthesis route is as follows: ； Includes the following steps: Step 1: Using compound of formula 1 and trimethylethynylsilane as raw materials, and palladium dichloride of bistriphenylphosphine as catalyst, after a coupling reaction with sage, TMS is removed with potassium fluoride as base to obtain intermediate 3. Step 2: Using S8 as the sulfur source, and any one of potassium carbonate, potassium acetate, cesium carbonate, cesium acetate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, dipotassium hydrogen phosphate, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, and 4-dimethylaminopyridine as the base, intermediate 3 underwent a cascade cyclization reaction to synthesize a series of fused-ring thiophene-like small molecule materials; The Ar is selected from any one of aryl and heteroaryl groups; the substituent R is one or more of hydrogen, halogen, C1-C30 alkyl, C1-C30 alkoxy, trifluoromethyl, trifluoromethoxy, hydroxyl, aryl, acyl, ester, nitro, amino, and (C1-C30 alkyl)amine.

2. The method for preparing the asymmetric diaryltrithiophene small molecule material as described in claim 1, characterized in that, The amount of bis(triphenylphosphine)-palladium dichloride catalyst added is 0.02-0.20 equivalents of the initial reactant amount.

3. The method for preparing the asymmetric diaryltrithiophene small molecule material as described in claim 1, characterized in that, The coupling reaction conditions for the sage were as follows: nitrogen gas was purged through a mixed solvent of triethylamine and tetrahydrofuran to remove oxygen; 1 equivalent of compound 1, 1.5 equivalents of compound 2, 0.03 equivalents of palladium dichloride catalyst (triphenylphosphine), and 0.06 equivalents of cuprous iodide catalyst were added to the system; and the reaction was carried out at 30°C. o The reaction was carried out at C for 5 hours; the volume ratio of the triethylamine and tetrahydrofuran in the mixed solvent was 1:

1.

4. The method for preparing the asymmetric diaryltrithiophene small molecule material as described in claim 1, characterized in that, The cascade cyclization reaction conditions are as follows: 1 equivalent of compound 3, 1 equivalent of potassium carbonate and 0.5 equivalent of S8 are added to the solvent N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, and the reaction is carried out at 145°C for 48 hours.

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