A thiazole imide compound and a preparation method thereof, a thiazole imide polymer and a preparation method thereof, and an optoelectronic device

Abstract

The present application relates to the field of organic synthesis and organic semiconductor, and particularly relates to a thiazole imide compound and a preparation method thereof, a thiazole imide polymer and a preparation method thereof and an optoelectronic device. A structural formula of the thiazole imide compound is shown in formula 1: wherein X is selected from a fluorine atom, a chlorine atom or a cyano group, Y is selected from an oxygen atom, a sulfur atom or a selenium atom, Q is selected from a bromine atom or an iodine atom, and R is selected from a substituted or unsubstituted C1-C60 alkyl group. The thiazole imide compound provided by the present application has excellent planarity and a lower LUMO energy level, can be copolymerized with a unit having electron-rich or electron-deficient properties, constructs a D-A type or A-A type n-type pi-conjugated polymer, can effectively regulate the photophysical and chemical properties of the molecule, and is further applied to the development of organic field effect transistors, organic photovoltaics, perovskite batteries and organic thermoelectric materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic synthesis and organic semiconductors, and in particular to a thiazole imine compound and a preparation method thereof, a thiazole imine polymer and a preparation method thereof, and an optoelectronic device. BACKGROUND

[0002] Polymeric semiconductors have been widely studied in organic electronic devices due to their light weight, solution processability and mechanical flexibility. With the development of new polymeric semiconductors, the device performance of the materials has been greatly improved. Among these polymeric semiconductors, the types and device performance of p-type semiconductors are much higher than those of n-type semiconductors, mainly because there are fewer strong electron-deficient polymerization units for constructing n-type polymeric semiconductors, and the synthesis is difficult. In order to balance the development between p-type and n-type polymers, it is of great significance to develop new electron-deficient units and apply them to construct high-performance n-type polymeric semiconductors.

[0003] Therefore, the prior art still needs to be improved and developed. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a thiazole imine compound and a preparation method thereof, a thiazole imine polymer and a preparation method thereof, and an optoelectronic device, aiming to provide a new electron-deficient unit for constructing n-type polymeric semiconductors. The electron-deficient unit based on the thiazole imine structure provided by the present application can be applied to construct high-performance n-type polymeric semiconductors.

[0005] The technical scheme of the present application is as follows:

[0006] In a first aspect of the present application, a thiazole imine compound is provided, wherein the structural formula of the thiazole imine compound is shown as formula 1:

[0007]

[0008] wherein,

[0009] X is selected from a fluorine atom, a chlorine atom or a cyano group, Y is selected from an oxygen atom, a sulfur atom or a selenium atom, and Q is selected from a bromine atom or an iodine atom;

[0010] R is selected from a substituted or unsubstituted C1-C60 alkyl group.

[0011] In a second aspect of the present application, a preparation method of a thiazole imine compound is provided, wherein when X is a cyano group and Q is a bromine atom, the synthesis route of the thiazole imine compound is as follows:

[0012] The preparation method of the thiazole imine compound comprises the following steps:

[0013] reacting the compound L1 and acetic anhydride at a first temperature for a first predetermined time to obtain a compound L2;

[0014] reacting the compound L2, R-NH2, 4-dimethylaminopyridine and a second organic solvent at a second temperature for a second predetermined time, and then adding acetic anhydride to react at a third temperature for a third predetermined time to obtain a compound L3;

[0015] reacting the compound L3, a cyano-containing salt and a fourth organic solvent at a fourth temperature for a fourth predetermined time to obtain a compound L4;

[0016] mixing the compound L4, a brominating agent and a fifth organic solvent, and then adding a Grignard reagent to react at a fifth temperature for a fifth predetermined time to obtain a thiazole imide compound L5.

[0017] In a third aspect of the present application, there is provided a method for preparing a thiazole imide compound, wherein, when X is a fluorine atom or a chlorine atom, and Q is a bromine atom, a synthesis route of the thiazole imide compound is as follows:

[0018] The method for preparing the thiazole imide compound comprises the steps of:

[0019] reacting the compound Y1 and acetic anhydride at a first temperature for a first predetermined time to obtain a compound Y2;

[0020] reacting the compound Y2, R-NH2, 4-dimethylaminopyridine and a second organic solvent at a second temperature for a second predetermined time, and then adding acetic anhydride to react at a third temperature for a third predetermined time to obtain a compound Y3;

[0021] mixing the compound Y3, a brominating agent and a fifth organic solvent, and then adding a Grignard reagent to react at a fifth temperature for a fifth predetermined time to obtain a thiazole imide compound Y4.

[0022] In a fourth aspect of the present application, there is provided a thiazole imide polymer, wherein a structural formula of the thiazole imide polymer is as shown in Formula 2:

[0023]

[0024] wherein,

[0025] n is an integer from 1 to 50;

[0026] X is selected from a fluorine atom, a chlorine atom or a cyano group, and Y is selected from an oxygen atom, a sulfur atom or a selenium atom;

[0027] R is selected from a substituted or unsubstituted C1-C60 alkyl group;

[0028] Ar is selected from a vinyl group, an ethynyl group, a substituted or unsubstituted C6-C100 aryl group, or a substituted or unsubstituted C4-C100 heteroaryl group, the heteroaryl group comprising at least one heteroatom selected from N, O, S and Se.

[0029] In a fifth aspect of the present application, a preparation method of a thiazole imide polymer is provided, comprising the step of: reacting a compound of Formula 1, a compound Z, a palladium catalyst and a sixth organic solvent at a sixth temperature for a sixth predetermined time to obtain a compound of Formula 2, the reaction formula being as follows:

[0030]

[0031] wherein X is selected from a fluorine atom, a chlorine atom or a cyano group, Y is selected from an oxygen atom, a sulfur atom or a selenium atom, and Q is selected from a bromine atom or an iodine atom;

[0032] R is selected from a substituted or unsubstituted C1-C60 alkyl group, and R2 is a methyl group or a n-butyl group;

[0033] n is an integer from 1 to 50;

[0034] Ar is selected from a vinyl group, an ethynyl group, a substituted or unsubstituted C6-C100 aryl group, or a substituted or unsubstituted C4-C100 heteroaryl group, the heteroaryl group comprising at least one heteroatom selected from N, O, S and Se.

[0035] In a sixth aspect of the present application, an optoelectronic device is provided, comprising an optoelectronic material layer, the optoelectronic material layer comprising the thiazole imide polymer according to the present application.

[0036] Beneficial effects: The present application connects structures such as furan, thiophene and selenophene on the thiazole imide structure, which on the one hand has a certain regulation effect on the energy level of the molecule, and on the other hand also enriches the types of electron-deficient units. And by introducing electron-withdrawing groups such as fluorine, chlorine and cyano on the furan, thiophene or selenophene structure to functionalize and modify the molecule, the solubility of the molecule is ensured, and the frontier orbital energy level of the molecule can be reduced, so that an electron-deficient building block with low energy level is obtained. The thiazole imide compound provided by the present application can be copolymerized with units with rich electron or electron-deficient units to construct D-A type or A-A type n-type π-conjugated polymers, which can effectively regulate the optical and chemical properties of the molecule, and then be applied to the development of organic field effect transistors, organic photovoltaics, perovskite batteries and organic thermoelectric materials. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 is a hydrogen spectrum of compound C1.

[0038] Figure 2 is a carbon spectrum of compound C1.

[0039] Figure 3 is a hydrogen spectrum of compound E1.

[0040] Figure 4 is a carbon spectrum of compound E1.

[0041] Figure 5 is a hydrogen spectrum of compound L13.

[0042] Figure 6 is a carbon spectrum of compound L13.

[0043] Figure 7 is a hydrogen spectrum of compound L14.

[0044] Figure 8 is a carbon spectrum of compound L14.

[0045] Figure 9 is a hydrogen spectrum of thiazole imide compound 8.

[0046] Figure 10 is a carbon spectrum of thiazole imide compound 8.

[0047] Figure 11 (a) of FIG. is an output characteristic curve of an organic field effect transistor device in Example 3, Figure 11 (b) of FIG. is a transfer characteristic curve of an organic field effect transistor device in Example 3.

[0048] Figure 12 is an organic thermoelectric performance curve of an organic thermoelectric device in Example 4. DETAILED DESCRIPTION

[0049] The present application provides a thiazole imide compound, a preparation method thereof, a thiazole imide polymer, a preparation method thereof, and an optoelectronic device. In order to make the purpose, technical scheme and effect of the present application more clear and definite, the present application is further described in detail below. It should be understood that the specific examples described herein are only used to explain the present application and are not used to limit the present application.

[0050] According to one embodiment of the present application, a thiazole imide compound is provided, wherein the thiazole imide compound has a structural formula as shown in formula 1:

[0051]

[0052] wherein,

[0053] X is selected from a fluorine atom, a chlorine atom or a cyano group, Y is selected from an oxygen atom, a sulfur atom or a selenium atom, and Q is selected from a bromine atom or an iodine atom;

[0054] R is selected from a substituted or unsubstituted C1-C60 alkyl group.

[0055] R in the embodiments of the present application is selected from substituted or unsubstituted C1-C60 alkyl, wherein the alkyl includes linear alkyl and branched alkyl, and wherein C1-C60 refers to the number of carbon atoms in the main chain of the alkyl, and the alkyl is not limited to having branches. R in the embodiments of the present application can be selected from substituted C1-C60 alkyl or unsubstituted C1-C60 alkyl, and when R is selected from substituted C1-C60 alkyl, the alkyl can be substituted with one or more selected from deuterium, halogen, or unsubstituted C1-C60 alkyl. In addition, when "substituted or unsubstituted C1-C60 alkyl" appears again below, it is not explained again as described in the embodiments.

[0056] The embodiments of the present application construct an electron-deficient unit of an n-type polymer having a structure of Formula 1 based on a thiazole imine structure. The thiazole imine has S and N interactions, so that the molecular skeleton thereof has good planarity, which is advantageous for carrier transport. However, the LUMO level of the thiazole imine is not low enough, which is not advantageous for constructing an n-type polymer. The embodiments of the present application connect structures such as furan, thiophene, and selenophene to the thiazole imine structure. These structures have a certain regulating effect on the energy level of the molecule, and also enrich the types of electron-deficient units. In addition, the molecule is functionally modified by introducing electron-withdrawing groups such as fluorine, chlorine, and cyano to the furan, thiophene, or selenophene structure, which ensures the solubility of the molecule and also lowers the frontier orbital energy level of the molecule, thereby obtaining an electron-deficient building unit having a low energy level.

[0057] The thiazole imine compound provided by the embodiments of the present application can be copolymerized with a unit having electron-rich or electron-deficient properties to construct a D-A type or A-A type n-type π-conjugated polymer, which can effectively regulate the optical and chemical properties of the molecule, and is further applied to the development of organic field effect transistors, organic photovoltaics, perovskite batteries, and organic thermoelectric materials.

[0058] According to an embodiment of the present application, R is selected from substituted or unsubstituted C1-C20 alkyl. Preferably, R is selected from substituted or unsubstituted C1-C12 alkyl.

[0059] According to an embodiment of the present application, X is a cyano group.

[0060] According to an embodiment of the present application, Y is an oxygen atom or a sulfur atom.

[0061] According to an embodiment of the present application, Q is a bromine atom.

[0062] According to an embodiment of the present application, the thiazole imine compound is selected from any one of Compound 1 to Compound 9:

[0063]

[0064]

[0065] According to one embodiment of the present application, there is provided a method for preparing the thiazole imide compound according to the present application, wherein when X is cyano and Q is bromine atom, the synthesis route of the thiazole imide compound is as follows:

[0066]

[0067] The method for preparing the thiazole imide compound comprises the steps of:

[0068] S1, reacting the compound L1 and acetic anhydride at a first temperature for a first predetermined time to obtain a compound L2;

[0069] S2, reacting the compound L2, R-NH2, 4-dimethylaminopyridine and a second organic solvent at a second temperature for a second predetermined time, then adding acetic anhydride at a third temperature for a third predetermined time to obtain a compound L3;

[0070] S3, reacting the compound L3, a cyanide-containing salt and a fourth organic solvent at a fourth temperature for a fourth predetermined time to obtain a compound L4;

[0071] S4, mixing the compound L4, a brominating agent and a fifth organic solvent, then adding a Grignard reagent at a fifth temperature for a fifth predetermined time to obtain a thiazole imide compound L5.

[0072] In step S1, in one embodiment, the first temperature is 100-150°C, and the first predetermined time is 1-12h.

[0073] In step S2, in one embodiment, the second temperature is 30-70°C, and the second predetermined time is 1-12h.

[0074] In one embodiment, the second organic solvent is dimethyl sulfoxide or dichloromethane, preferably dichloromethane, but not limited thereto.

[0075] In one embodiment, the third temperature is 100-150°C, and the third predetermined time is 1-12h.

[0076] In step S3, in one embodiment, the cyanide-containing salt includes cuprous cyanide and zinc cyanide, preferably cuprous cyanide, but not limited thereto.

[0077] In an embodiment, the fourth organic solvent includes one or more of dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, and toluene, preferably N,N-dimethylformamide, but is not limited thereto.

[0078] In an embodiment, the fourth temperature is 70°C-120°C, for example, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C, preferably 100°C.

[0079] In an embodiment, the fourth predetermined time is 12h-24h.

[0080] In step S4, in an embodiment, the brominating agent is dibromotetrachloroethane, N-bromosuccinimide, liquid bromine, or the like, preferably dibromotetrachloroethane, but is not limited thereto.

[0081] In an embodiment, the fifth organic solvent is tetrahydrofuran or methyltetrahydrofuran, preferably tetrahydrofuran, but is not limited thereto.

[0082] In an embodiment, the Grignard reagent is diisopropylamine lithium or lithium bis(trimethylsilyl)amide, preferably lithium bis(trimethylsilyl)amide, but is not limited thereto.

[0083] In an embodiment, the fifth temperature is 0°C--78°C, and the fifth predetermined time is 0.2h-0.5h.

[0084] According to an embodiment of the present application, there is provided a method for preparing the thiazole imide compound according to the present application, wherein, when X is a fluorine atom or a chlorine atom, and Q is a bromine atom, a synthesis route of the thiazole imide compound is as follows:

[0085] The method for preparing the thiazole imide compound includes the steps of:

[0086] S11, reacting compound Y1 and acetic anhydride at a first temperature for a first predetermined time to obtain compound Y2;

[0087] S12, reacting the compound Y2, R-NH2, 4-dimethylaminopyridine, and a second organic solvent at a second temperature for a second predetermined time, and then adding acetic anhydride at a third temperature for a third predetermined time to obtain compound Y3;

[0088] S13, mixing the compound Y3, a brominating agent, and a fifth organic solvent, and then adding a Grignard reagent at a fifth temperature for a fifth predetermined time to obtain thiazole imide compound Y4.

[0089] In step S11, in an embodiment, the first temperature is 100-150°C, and the first predetermined time is 1-12h.

[0090] In step S12, in an embodiment, the second temperature is 30-70°C, and the second predetermined time is 1-12h.

[0091] In an embodiment, the second organic solvent is dimethyl sulfoxide or dichloromethane, preferably dichloromethane, but not limited thereto.

[0092] In an embodiment, the third temperature is 100-150°C, and the third predetermined time is 1-12h.

[0093] In step S13, in an embodiment, the brominating agent is dibromotetrachloroethane, N-bromosuccinimide, liquid bromine, etc., preferably dibromotetrachloroethane, but not limited thereto.

[0094] In an embodiment, the fifth organic solvent is tetrahydrofuran or methyl tetrahydrofuran, preferably tetrahydrofuran, but not limited thereto.

[0095] In an embodiment, the format agent is lithium diisopropylamide or lithium bis(trimethylsilyl)amide, preferably lithium bis(trimethylsilyl)amide, but not limited thereto.

[0096] In an embodiment, the fifth temperature is 0- -78°C, and the fifth predetermined time is 0.2-0.5h.

[0097] According to an embodiment of the present application, the synthesis route of the compound L1 or compound Y1 is as follows:

[0098]

[0099] In this embodiment, the preparation method of compound B by reacting compound A includes mixing compound A and tetrahydrofuran, adding isopropyl magnesium bromide under low temperature conditions (low temperature conditions are 0°C, -10°C, -20°C, -40°C, -60°C, -78°C, etc., preferably 0°C) for 5h, continuously adding propyl chloroformate under low temperature for 0.5h, then slowly rising to room temperature and stirring overnight to obtain compound B.

[0100] In this embodiment, the preparation method of compound C by reacting compound B comprises: mixing compound B and tetrahydrofuran, adding TMPMgCl.LiCl under low temperature conditions (the low temperature conditions are 0℃, -10℃, -20℃, -40℃, -60℃, -78℃, etc., and preferably -20℃) for 0.5h, continuously adding tributyltin chloride under low temperature for 0.5h, then slowly rising to room temperature and stirring overnight to obtain compound C.

[0101] In this embodiment, the preparation method of compound E by reacting compound C and compound D comprises: mixing compound C, compound D, a palladium catalyst (the palladium catalyst is tetraphenylphosphine palladium and dichlorobistriphenylphosphine palladium, etc., and preferably tetraphenylphosphine palladium), CuI and DMF, and reacting at 110℃ for 24h to obtain compound E.

[0102] In this embodiment, the preparation method of compound L1 or compound Y1 by reacting compound E comprises: mixing compound E, sodium hydroxide (or potassium hydroxide) and tetrahydrofuran at 70℃ and reacting overnight, and then acidifying with hydrochloric acid to obtain compound L1 or compound Y1.

[0103] According to one embodiment of the present application, a thiazole imine polymer is provided, wherein the thiazole imine polymer has a structural formula as shown in formula 2:

[0104]

[0105] wherein,

[0106] n is an integer from 1 to 50;

[0107] X is selected from a fluorine atom, a chlorine atom or a cyano group, and Y is selected from an oxygen atom, a sulfur atom or a selenium atom;

[0108] R is selected from a substituted or unsubstituted C1-C60 alkyl group;

[0109] Ar is selected from a vinyl group, an ethynyl group, a substituted or unsubstituted C6-C100 aryl group or a substituted or unsubstituted C4-C100 heteroaryl group, and the heteroaryl group contains at least one heteroatom selected from N, O, S and Se.

[0110] The thiazole imine polymer is obtained by copolymerizing a thiazole imine compound with an Ar unit having electron-rich or electron-deficient properties, and is an excellent n-type polymer semiconductor, which can be applied to optoelectronic devices such as organic field effect transistors, organic photovoltaic devices, perovskite photovoltaic devices or organic thermoelectric devices.

[0111] According to one embodiment of the present application, the Ar is selected from any one of the following structures:

[0112]

[0113] wherein the dotted line in the structure represents a bond of the structure, R1is selected from substituted or unsubstituted C1-C60alkyl.

[0114] According to an embodiment of the present application, the thiazole imine polymer has a structure of:

[0115]

[0116] According to an embodiment of the present application, there is provided a method for preparing a thiazole imine polymer, comprising the step of: reacting a compound of Formula 1, a compound Z, a palladium catalyst, and a sixth organic solvent at a sixth temperature for a sixth predetermined time to obtain a compound of Formula 2, the reaction formula being as follows:

[0117]

[0118] wherein X is selected from a fluorine atom, a chlorine atom, or a cyano group, Y is selected from an oxygen atom, a sulfur atom, or a selenium atom, and Q is selected from a bromine atom or an iodine atom;

[0119] R is selected from substituted or unsubstituted C1-C60alkyl, and R2is a methyl group or a n-butyl group;

[0120] n is an integer of 1-50;

[0121] Ar is selected from a vinyl group, an ethynyl group, a substituted or unsubstituted C6-C100aryl group, or a substituted or unsubstituted C4-C100heteroaryl group, the heteroaryl group comprising at least one heteroatom selected from N, O, S, and Se.

[0122] According to an embodiment of the present application, the palladium catalyst is a combination of tris(dibenzylideneacetone)dipalladium and tri(o-methylphenyl)phosphine.

[0123] In a preferred embodiment, the molar amount of the tris(dibenzylideneacetone)dipalladium is 1%-4% of the total molar amount of the palladium catalyst, for example, 1.5%, 2%, 2.5%, 3%, 4%, etc., and more preferably 3%.

[0124] In a preferred embodiment, the molar amount of the tri(o-methylphenyl)phosphine is 10%-25% of the total molar amount of the palladium catalyst, for example, 10%, 15%, 20%, 21%, 22%, 23%, 24%, 25%, etc., and more preferably 24%.

[0125] According to an embodiment of the present application, the sixth solvent is toluene.

[0126] According to one embodiment of the present application, the sixth temperature is 100-140°C, for example 100°C, 110°C, 120°C, 130°C, 140°C, etc., preferably 140°C.

[0127] According to one embodiment of the present application, the sixth predetermined time is 1-4h.

[0128] According to one embodiment of the present application, there is provided an optoelectronic device, comprising a layer of optoelectronic material, the layer of optoelectronic material comprising a thiazole-imide polymer as described above. The optoelectronic device is an organic field effect transistor, an organic photovoltaic device, a perovskite photovoltaic device or an organic thermoelectric device.

[0129] The present application is further illustrated by the following specific examples.

[0130] Example 1

[0131] This example provides a thiazole-imide compound 8 and a preparation method thereof, wherein the structural formula of the thiazole-imide compound 8 is as follows: The preparation method of the thiazole-imide compound 8 comprises the following steps:

[0132] (1) Synthesis of compound B1

[0133]

[0134] Under an argon atmosphere, compound A1 (5 g, 20.7 mmol), re-distilled THF (60 mL) were added to a dry single-necked flask (250 mL) equipped with a stir bar, and the reaction system was kept in an inert gas atmosphere, and the mixed reaction liquid was placed in a 0°C ice water bath and stirred. Then i-PrMgBr (25.9 mL, 25.9 mmol) was added dropwise to the reaction system, and after the dropwise addition was completed, it was kept at 0°C for 5h. Then continue to keep low temperature, propyl chloroformate (4.7 mL, 41.4 mmol) was added dropwise to the reaction system. After the addition of propyl chloroformate was completed, continue to keep at this temperature for 0.5h. Finally, slowly rise to room temperature and stir overnight. Before treating the reaction, first quench the reaction by adding water, then remove the THF, extract, dry and filter. Finally, use a silica gel chromatographic column for purification to obtain the oily liquid product compound B1, with a yield of 80%.

[0135] The hydrogen spectrum and carbon spectrum attribution results of the compound B1 are as follows:

[0136] 1H NMR (400 MHz, CDCI3) δ (ppm): 8.11 (d, J = 3.6 Hz, 1 H), 7.31 (d, J = 3.6 Hz, 1 H), 4.25 (t, J = 6.6 Hz, 2 H), 1.78 (dt, J = 14.1, 7.1 Hz, 2 H), 1.02 (t, J = 7.4 Hz, 3 H). 13 C NMR (126 MHz, CDCI3) δ (ppm): 161.49, 134.16, 131.53, 125.28, 110.82, 66.65, 22.04, 10.59.

[0137] (2) Synthesis of compound C1

[0138]

[0139] Compound B1 (0.5 g, 2 mmol), redistilled THF (40 mL) were added to a dry single-mouthed flask equipped with a stirrer under argon atmosphere, keeping the reaction system in an inert gas atmosphere, and the mixed reaction liquid was placed in a -20 °C low-temperature bath and stirred. Then TMPMgCl-LiCl (2.4 mL, 2.4 mmol) was added dropwise to the reaction system, and after the dropwise addition was completed, it was kept at -20 °C for 0.5 h. Then, while keeping the temperature low, tributyltin chloride (0.87 mL, 3 mmol) was added dropwise to the reaction system, and then it was kept at 0 °C for 0.5 h. Finally, it was allowed to react at room temperature and stirred overnight. After the reaction was completed, water was added to quench the reaction, then THF was removed, and extraction, drying and filtration were performed. Finally, purification was performed using a silica gel chromatographic column to obtain the product compound C1 as a viscous oily liquid, with a yield of 90%.

[0140] The hydrogen spectrum and carbon spectrum assignment results of the compound C1 are as follows Figure 1 is the hydrogen spectrum of compound C1, Figure 2 is the carbon spectrum of compound C1):

[0141] 1 H NMR (400 MHz, CDCI3) δ (ppm): 7.57-7.50 (m, 1 H), 4.26 (t, J = 6.7 Hz, 2 H), 1.81 (dt, J = 14.3, 7.2 Hz, 2 H), 1.55-1.46 (m, 6 H), 1.34-1.28 (m, 6 H), 1.18-1.10 (m, 6 H), 1.05 (d, J = 7.4 Hz, 3 H), 0.88 (t, J = 7.3 Hz, 9 H). 13C NMR (126 MHz, CDCI3) δ (ppm): 163.85, 153.23, 137.13, 131.16, 111.52, 66.95, 28.95, 27.25, 22.07, 13.65, 11.75, 10.68.

[0142] (3) Synthesis of compound E1

[0143]

[0144] Compound C1 (1.22 g, 2.3 mmol), compound D1 (0.68 g, 0.9 mmol), Pd(PPh3)4(104 mg, 0.09 mmol) and Cul (10 mg) were added into a round bottom flask with a stirrer and a condenser under argon atmosphere, then DMF was added into the flask and heated to 110 °C for 24 h. After the reaction was completed, the DMF was removed, then extracted, dried, filtered and finally purified by silica gel column chromatography to obtain the product compound E1 as a light yellow solid with a yield of 70%.

[0145] The hydrogen spectrum and carbon spectrum attribution results of the compound E1 are as follows Figure 3 is the hydrogen spectrum of compound E1, Figure 4 is the carbon spectrum of compound E1):

[0146] 1 H NMR (400 MHz, CDCI3) δ (ppm): 7.47 (s, 2H), 4.09 (dd, J = 14.1, 6.3 Hz, 8H), 1.57-1.46 (m, 6H), 1.28-1.07 (m, 32H), 0.87 (td, J = 6.8, 1.5 Hz, 12H), 0.80 (t, J = 7.4 Hz, 6H). 13 CNMR (101 MHz, CDCI3) δ (ppm): 161.26, 160.87, 159.62, 145.23, 137.46, 135.47, 132.25, 126.28, 111.72, 68.67, 67.15, 37.12, 31.87, 30.92, 30.59, 29.59, 28.85, 26.64, 22.94, 22.69, 21.71, 14.13, 10.34.

[0147] (4) Synthesis of compound L11

[0148]

[0149] Compound E1 (5 g, 4.6 mmol), NaOH (1.47 g, 36.8 mmol) were added into a two-necked round bottom flask equipped with a stir bar and a condenser, followed by THF (50 mL) and H2O (10 mL), and the reaction mixture was heated to 70 °C and stirred overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and then THF was removed by a rotary evaporator. A small amount of water was added and stirred, and then HCl was added dropwise until the solution became acidic, and a solid was precipitated. The solid was filtered and washed with deionized water five times, and then the solid was dried in a vacuum oven at 60 °C for 12 h to obtain a yellow solid product, compound L11.

[0150] (5) Synthesis of compound L12

[0151]

[0152] Compound L11 was added into a two-necked round bottom flask equipped with a stir bar and a condenser, followed by acetic anhydride, and then the flask was placed in an oil bath at 140 °C and stirred for 12 h. After the reaction was completed, a large amount of yellow solid was precipitated. The solid was filtered, washed with methanol, and then dried in a vacuum oven to obtain a yellow solid product, compound L12.

[0153] (6) Synthesis of compound L13

[0154]

[0155] Compound L12 (100 mg, 0.16 mmol), DMAP (58 mg, 0.47 mmol), and 2-octyldodecylamine (141 mg, 0.47 mmol) were added into a two-necked round bottom flask equipped with a stir bar and a condenser under an argon atmosphere, and then dry CH2Cl2was added, and the reaction mixture was placed in an oil bath at 50 °C and stirred overnight. After the reaction was completed, CH2Cl2was removed, and then acetic anhydride (8 mL) was added under an argon atmosphere and refluxed for 3 h. After the reaction was completed, acetic anhydride was removed, and then methanol was added, and a solid was precipitated. The solid was filtered and purified by a silica gel column to obtain a dark yellow solid product, compound L13, with a yield of 60%.

[0156] The hydrogen spectrum and carbon spectrum assignment results of the compound L13 are as follows Figure 5 is the hydrogen spectrum of compound L13, Figure 6 is the carbon spectrum of compound L13):

[0157] 1H NMR (500 MHz, CDC13) δ (ppm): 7.51 (s, 2H), 4.21 (d, J = 7.2 Hz, 4H), 1.91 (d, J = 5.5 Hz, 2H), 1.22 (s, 64H), 0.86 (td, J = 6.9, 3.7 Hz, 12H). 13 C NMR (126 MHz, CDC13) δ (ppm): 13C NMR (126 MHz, CDC13) δ (ppm): 162.50, 159.89, 157.56, 146.22, 135.25, 132.75, 132.38, 126.72, 114.67, 51.40, 36.84, 31.94, 31.70, 29.99, 29.69, 29.63, 29.58, 29.39, 29.35, 26.46, 22.71, 14.16.

[0158] (7) Synthesis of compound L14

[0159]

[0160] Compound L13 (1 g, 0.84 mmol) and CuCN (600 mg, 6.7 mmol) were added into a two-necked round bottom flask with a stirrer and a condenser under argon atmosphere, and then dry DMF was added. The reaction system was placed in a 100 °C oil bath and stirred overnight. After the reaction was completed, the solvent was removed, and then extraction, drying, filtration, and finally purification by silica gel column chromatography were performed to obtain yellow solid product compound L14 with a yield of 30%.

[0161] The hydrogen spectrum and carbon spectrum assignment results of the compound L14 are as follows Figure 7 is the hydrogen spectrum of compound L14, Figure 8 is the carbon spectrum of compound L14):

[0162] 1 H NMR (500 MHz, CDC13) δ (ppm): 8.12 (s, 2H), 4.28 (d, J = 7.3 Hz, 4H), 1.99-1.92 (m, 2H), 1.27 (d, J = 43.9 Hz, 64H), 0.85 (td, J = 6.8, 3.2 Hz, 12H). 13C NMR (126 MHz, CDC13) δ (ppm): 160.26, 159.35, 157.81, 146.71, 137.87, 134.68, 133.89, 133.42, 116.73, 113.14, 51.00, 31.94, 31.93, 31.61, 30.06, 29.69, 29.68, 29.64, 29.59, 29.39, 29.34, 26.40, 22.71, 14.16.

[0163] (8) Synthesis of thiazole imide compound 8

[0164]

[0165] Compound L14 (0.54 g, 0.5 mmol) and dibromotetrachloroethane (0.65 g, 2 mmol) were added to a stirred Erlenmeyer flask under argon atmosphere, argon atmosphere was maintained, and re-distilled THF (60 mL) was added to the reaction system, and the raw material was stirred to be completely dissolved. After complete dissolution, the Erlenmeyer flask was placed in a low-temperature bath at -78°C, and when the temperature was lowered to -78°C, lithium bis(trimethylsilyl)amide (4 mL, 4 mmol) was added dropwise to the reaction system to react, and after the dropwise addition was completed, the reaction was allowed to proceed for 10 min at low temperature. After the reaction was completed, the reaction was quenched with saturated ammonium chloride solution at low temperature. After the reaction was allowed to rise to room temperature, the THF solvent was removed with a rotary evaporator. After extraction, drying, and filtration, the final product, thiazole imide compound 8, was obtained as a dark yellow solid with a yield of 20% by silica gel column chromatography.

[0166] The hydrogen spectrum and carbon spectrum assignment results of the thiazole imide compound 8 are as follows Figure 9 is the hydrogen spectrum of thiazole imide compound 8, Figure 10 is the carbon spectrum of thiazole imide compound 8):

[0167] 1 H NMR (500 MHz, CDC13) δ (ppm): 4.28 (d, J = 7.3 Hz, 2H), 1.98-1.92 (m, 1H), 1.40-1.19 (m, 32H), 0.87 (td, J = 7.0, 2.5 Hz, 6H).

[0168] 13C NMR (126 MHz, CDCI3) δ (ppm): 159.40, 159.13, 157.82, 146.76, 134.21, 133.79, 133.71, 127.62, 119.27, 112.24, 51.21, 36.42, 31.94, 31.58, 30.06, 29.70, 29.65, 29.60, 29.40, 29.36, 26.37, 22.72, 14.16.

[0169] Example 2

[0170] The present example provides a thiazole imide polymer PTzICN-BTI and a preparation method thereof, wherein the structural formula of the thiazole imide polymer PTzICN-BTI is as follows: The reaction formula of the preparation method is as follows:

[0171]

[0172] The specific preparation method is as follows: under the protection of argon, thiazole imide compound 8 (49.6 mg, 0.04 mmol) and compound Z1 (43.8 mg, 0.04 mmol) are added into 3 mL of toluene, and then tris(dibenzylideneacetone)dipalladium (0.55 mg, 0.0006 mmol) and tris(o-tolyl)phosphine (P(o-tol)3), 1.46 mg, 0.0048 mmol) are added. The reaction mixture is heated to 80°C for 10 minutes, 100°C for 10 minutes, and 140°C for 3 hours. After the reaction is cooled to room temperature, it is poured into methanol and filtered. Methanol, acetone, n-hexane and dichloromethane are used for Soxhlet extraction to remove low molecular weight impurities, and then trichloromethane is used for Soxhlet extraction to obtain the thiazole imide polymer PTzICN-BTI, with a yield of 80%.

[0173] Example 3

[0174] The present example provides an organic field effect transistor device and a preparation method thereof, which are as follows: on a borosilicate glass, a source-drain electrode of 3 nm Cr / 30 nm Au is patterned by photolithography, with a channel length (L) of 10 μm, 20 μm, 50 μm and 100 μm, and a channel width (W) of 5 mm. Subsequently, a polymer active layer (a photoelectric material layer, the thiazole imide polymer PTzICN-BTI prepared in Example 2, with a thickness of 30 nm) is spin-coated onto the substrate, and annealed at 200°C for 10 minutes. Then, about 400 nm thick perfluoro(1-butenyl vinyl ether) polymer is spin-coated on the polymer active layer, and annealed at 100°C for 15 minutes. Finally, 50 nm thick aluminum is evaporated onto the uppermost layer to complete the device preparation.

[0175] The output characteristic curve and the transfer characteristic curve of the organic field effect transistor device in Example 3 were tested in the following manner. In an inert gas-filled glove box, the prepared organic field effect transistor device was placed on a probe station. The source electrode, the drain electrode and the gate electrode were connected, respectively. By applying different gate voltages (V G ), the curve of the source-drain current (I SD ) versus the source-drain voltage (V SD ) was obtained, which was the output characteristic curve. Subsequently, the curve of I SD versus V G was measured at different V SD , and the transfer characteristic curve was obtained.

[0176] Figure 11 Figure (a) in the drawing is the output characteristic curve of the organic field effect transistor device in Example 3, Figure 11 Figure (b) in the drawing is the transfer characteristic curve of the organic field effect transistor device in Example 3. According to the figure, the electron mobility of the thiazole imide polymer PTzICN-BTI is 1.32 cm 2 V -1 s -1 , which shows a single n-type electron migration characteristic.

[0177] Example 4

[0178] The present example provides an organic thermoelectric device and a preparation method thereof, which are as follows.

[0179] (1) Cleaning of the glass substrate: the glass substrate was cleaned by isopropanol, acetone and isopropanol ultrasonic cleaning for 10 min, and then baked at 120℃ for 20 min. (2) Evaporation of the electrode: 30 nm of gold was evaporated as the electrode on both ends of the surface of the cleaned glass substrate by a vacuum evaporation machine. (3) Preparation of the gold nano layer: 0.1 nm of gold nanoparticles were evaporated by a vacuum evaporation instrument, and the gold nanoparticles served as a catalyst. (4) Preparation of the polymer thin film layer (photoelectric material layer): the thiazole imide polymer PTzICN-BTI prepared in Example 2 was spin-coated on the gold nano layer by a spin coating method, so as to obtain a polymer thin film layer with a thickness of 30 nm. (5) The dopant N-DMBI (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole) was prepared into a solution with a concentration of 1 mg / mL, and then spin-coated on the polymer thin film layer. (6) In order to enable the gold nanoparticles to quickly catalyze the doping, the glass sheet spin-coated with the dopant N-DMBI was placed on a heating table at 120℃ and heated for 10 s, so as to obtain the organic thermoelectric device.

[0180] The same preparation method of the organic thermoelectric device is adopted, and the only difference is that the concentration of the dopant N-DMBI in the (5)th step is adjusted to 0.1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL and 5 mg / mL.

[0181] The organic thermoelectric performance curve of the organic thermoelectric device in Example 4 is performed, and the specific test method is as follows: the thermoelectric device prepared in Example 4 is measured by a thermoelectric tester, and the thermoelectric voltage under different doping concentrations (0.1 mg / mL, 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL and 5 mg / mL) is measured. The Seebeck coefficient (S) under different doping concentrations can be obtained by calculation. Similarly, by testing the current-voltage curve under different doping concentrations using the same device, the electrical conductivity (σ) can be calculated. According to the power factor calculation formula PF=S 2 σ, the power factor under different doping concentrations can be calculated.

[0182] Figure 12 The organic thermoelectric performance curve of the organic thermoelectric device in Example 4 is performed, and according to the figure, the electrical conductivity of the thiazole imide polymer PTzICN-BTI is 24.6 S cm -1 , and the power factor of the thiazole imide polymer PTzICN-BTI is 19.1 μW m -1 K -2 .

[0183] It should be understood that the application of the present application is not limited to the above examples, and those skilled in the art can make improvements or changes according to the above description, and all these improvements and changes shall belong to the protection scope of the appended claims of the present application.

Claims

1. A thiazole imide compound, characterized by, The structural formula of the thiazole imine compound is shown as formula 1: Wherein, X is cyano, Y is selected from oxygen atom, sulfur atom or selenium atom, and Q is selected from bromine atom or iodine atom; R is selected from C1-C60 alkyl.

2. The thiazole imine compound according to claim 1, characterized by Y is oxygen atom or sulfur atom, Q is bromine atom, and R is selected from C1-C20 alkyl.

3. The thiazole imine compound according to claim 1, characterized by The thiazole imine compound is selected from any one of compound 7 to compound 9: ， ， 。 4. A process for preparing the thiazole imide compound according to claim 1, characterized by, When X is cyano and Q is bromine atom, the synthesis route of the thiazole imine compound is as follows: ， The preparation method of the thiazole imine compound comprises the steps of: reacting compound L1 and acetic anhydride at a first temperature for a first predetermined time to obtain compound L2; reacting the compound L2, R-NH2, 4-dimethylaminopyridine and a second organic solvent at a second temperature for a second predetermined time, then adding acetic anhydride at a third temperature for a third predetermined time to obtain compound L3; reacting the compound L3, a cyano-containing salt and a fourth organic solvent at a fourth temperature for a fourth predetermined time to obtain compound L4; mixing the compound L4, a brominating agent and a fifth organic solvent, then adding Grignard reagent at a fifth temperature for a fifth predetermined time to obtain thiazole imine compound L5.

5. A thiazolylimine polymer characterized by, The structural formula of the thiazole imine polymer is shown as formula 2: Wherein, n is an integer of 1-50; X is cyano, Y is selected from oxygen atom, sulfur atom or selenium atom; R is selected from C1-C60 alkyl; Ar is selected from vinyl, ethynyl, substituted or unsubstituted C6-C100 aryl or substituted or unsubstituted C4-C100 heteroaryl, the heteroaryl comprising at least one heteroatom selected from N, O, S and Se.

6. A thiazolylimine polymer characterized by, The structural formula of the thiazole imine polymer is shown as formula 2: Wherein, n is an integer of 1-50; X is cyano, Y is selected from oxygen atom, sulfur atom or selenium atom; R is selected from C1-C60 alkyl; Ar is selected from any one of the following structures: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ； Wherein, the dotted line in the structure represents the connecting bond of the structure, and R1 is selected from substituted or unsubstituted C1-C60 alkyl.

7. The thiazole imine polymer of claim 5, wherein The structural formula of the thiazole imine polymer is any one of the following structures: , , , 。 8. A process for the preparation of the thiazole imide polymer of claim 5, characterized by, The preparation method comprises the steps of: reacting the compound of formula 1, compound Z, a palladium catalyst and a sixth organic solvent at a sixth temperature for a sixth predetermined time to obtain the compound of formula 2, and the reaction formula is as follows: ， Wherein X is cyano, Y is selected from oxygen atom, sulfur atom or selenium atom, and Q is selected from bromine atom or iodine atom; R is selected from C1-C60 alkyl, and R2 is methyl or n-butyl; n is an integer of 1-50; Ar is selected from vinyl, ethynyl, substituted or unsubstituted C6-C100 aryl or substituted or unsubstituted C4-C100 heteroaryl, the heteroaryl comprising at least one heteroatom selected from N, O, S and Se.

9. An optoelectronic device, characterized in that The photoelectric material layer comprises the thiazole imine polymer according to any one of claims 5-7.

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