A tetraazaisoindigo derivative and its preparation method

Abstract

This invention discloses a tetraazaisoindigo derivative and its preparation method. The structural formula of the tetraazaisoindigo derivative is shown in formula (I): where X and Y are both selected from H or N. This invention improves the core structure of isoindigo by introducing a more electron-deficient pyrazine or pyrimidine ring to replace the original benzene ring in isoindigo, thereby enhancing its electron-withdrawing ability, lowering the HOMO / LUMO energy levels, and obtaining an organic semiconductor material with better electron transport performance.

Description

Technical Field

[0001] This invention belongs to the field of heterocyclic compound synthesis and organic semiconductor materials, and particularly relates to a tetraazaisoindigo derivative and its preparation method. Background Technology

[0002] Indigo-based materials possess good coplanarity, readily form favorable π-π stacking, and exhibit excellent environmental stability, making them widely used as important acceptor units in optoelectronic devices such as organic field-effect transistors and organic solar cells. However, when used as acceptor materials for constructing high-performance organic semiconductors, indigo-based materials are limited by their insufficient electron-withdrawing ability, resulting in high HOMO / LUMO energy levels and poor electron transport performance.

[0003] Currently, there is limited research on tetraazaisoindigo compounds. Therefore, conducting structural design and synthesis work based on tetraazaisoindigo compounds has significant research and application value in the field of organic optoelectronic materials. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a tetraazaisoindigo derivative and its preparation method, thereby solving the technical problem of poor electron transport performance of existing isoindigo materials.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides a tetraazaisoindigo derivative, the structural formula of which is shown in formula (I):

[0007] ,

[0008] Where X is N and Y is C or X is C and Y is N;

[0009] Ar1 is selected from , , , , , , , Any one of them;

[0010] Ar2 is selected from , , , , , , , Any one of them;

[0011] R is a single or multiple substituted functional group, wherein the functional group is any one of the following: a straight-chain alkyl group of C1-C24, a branched alkyl group of C1-C24, or an alkoxy group of C1-C24.

[0012] Preferably, the derivative has the structure shown in formula (II), formula (III), or formula (IV):

[0013] ,

[0014] ;

[0015] Wherein, R is a single or multiple substituted functional group, wherein the functional group is any one of the following: straight-chain alkyl, branched alkyl, and alkoxy groups of C1-C24.

[0016] This invention also provides a method for preparing a tetraazaisoindigo derivative, comprising the following steps:

[0017] (1) Compound 1 was subjected to bromination to obtain compound 2;

[0018] (2) Compound 2 was catalytically coupled with trimethylethynylsilane to obtain compound 3;

[0019] (3) Compound 3 was subjected to a cyclization reaction under organic or inorganic base conditions to obtain compound 4;

[0020] (4) Compound 4 and RX1 were subjected to alkylation under inorganic base conditions to obtain compound 5;

[0021] (5) Compound 5 is coupled with Ar1X2 or Ar2X2 under palladium catalysis to obtain compound 6-1 or compound 6-2;

[0022] (6) Reacting compound 6-1 or compound 6-2 with a bromine reagent in aqueous tert-butanol to obtain compound 7-1 or compound 7-2;

[0023] (7) Compound 7-1 was oxidized to obtain compound 8, and compound 7-2 was reduced to obtain compound 9;

[0024] (8) Compound 8 and compound 9 were refluxed under acidic conditions to obtain compound 10, which is the tetraazaisoindigo derivative;

[0025] The reaction synthesis route is shown below:

[0026]

[0027] Where X is N and Y is C or X is C and Y is N;

[0028] X1 is a halogen atom, and X2 is a borate group or a tin-containing group;

[0029] Ar1 is selected from , , , , , , , Any one of them;

[0030] Ar2 is selected from , , , , , , , Any one of them;

[0031] R is a single or multiple substituted functional group, wherein the functional group is any one of the following: a straight-chain alkyl group of C1-C24, a branched alkyl group of C1-C24, or an alkoxy group of C1-C24.

[0032] Preferably, in step (1), the brominating reagent used in the bromination reaction is at least one of NBS, dibromohydantoin, bromine water, and hydrobromic acid.

[0033] Preferably, in step (3), the organic base is at least one of sodium tert-butoxide, potassium tert-butoxide, and sodium ethoxide; and the inorganic base is at least one of potassium hydroxide and sodium hydroxide.

[0034] Preferably, in step (4), the inorganic base is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydride, and potassium hydride.

[0035] Preferably, in steps (2) and (5), the catalyst used in the coupling reaction is at least one of tetra(triphenylphosphine)palladium, tri(tri-p-methylphenylphosphine)palladium, tri(dibenzylideneacetone)palladium, bis(1,4-biphenylphosphine)butylpalladium dichloride, palladium acetate, and bis(triphenylphosphine)palladium dichloride.

[0036] Preferably, in step (6), the water content of tert-butanol is 1% to 10%; the brominating agent is at least one of NBS, dibromohydantoin, bromine water, and hydrobromic acid.

[0037] Preferably, in step (7), compound 7-1 is oxidized to obtain compound 8, and the oxidant used is silver nitrate, and the molar ratio of compound 7-1 to silver nitrate is 1:(2~15).

[0038] Compound 7-2 was reduced to obtain compound 9. The reducing agent used was zinc powder, and the molar ratio of compound 7-2 to zinc powder was 1:(5~20).

[0039] Preferably, in step (8), compound 8, compound 9 and p-toluenesulfonic acid are refluxed in acetic acid to obtain tetraazaisoindigo derivative.

[0040] The beneficial effects of this invention are:

[0041] This invention improves the core structure of isoindigo by introducing a more electron-deficient pyrazine or pyrimidine ring to replace the original benzene ring in isoindigo, thereby enhancing its electron-withdrawing ability and reducing the HOMO / LUMO energy levels of the conjugated polymer material, resulting in an organic semiconductor material with better electron transport performance.

[0042] This invention designs and synthesizes tetraazaisoindigo derivatives with different aromatic heterocyclic ends and different alkyl chain modifications. By flexibly introducing different aromatic heterocyclic ends into the molecule, the LUMO and HOMO energy levels of the molecule are changed, which to some extent alters the photoelectric properties of the molecule. At the same time, the introduction of alkyl chains of different lengths improves the solubility of the molecule (it can be dissolved in common solvents such as dichloromethane and chloroform).

[0043] The method for synthesizing the target molecule in this invention is simple, has a high yield, and is beneficial for the large-scale preparation of the product. Attached Figure Description

[0044] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings of the embodiments will be briefly described below.

[0045] Figure 1 The 1H NMR spectrum of compound 10a in Example 1 of this invention;

[0046] Figure 2 The carbon NMR spectrum of compound 10a in Example 1 of this invention;

[0047] Figure 3 The 1H NMR spectrum of compound 10b in Example 2 of this invention;

[0048] Figure 4 The carbon NMR spectrum of compound 10b in Example 2 of this invention;

[0049] Figure 5 The 1H NMR spectrum of compound 10c in Example 3 of this invention;

[0050] Figure 6 The carbon NMR spectrum of compound 10c in Example 3 of this invention;

[0051] Figure 7Optical spectra of compounds from Examples 1-3 and Comparative Example 1 in DCM; Figure 7 In the image, (a) is the ultraviolet absorption spectrum and (b) is the fluorescence emission spectrum.

[0052] Figure 8 The images show the cyclic voltammetry of the compounds in Examples 1-3 in DCM. Detailed Implementation

[0053] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0054] This invention provides a tetraazaisoindigo derivative, the structural formula of which is shown in formula (I):

[0055] ,

[0056] Where X is N and Y is C, or X is C and Y is N.

[0057] Ar1 is selected from , , , , , , , Any one of them;

[0058] Ar2 is selected from , , , , , , , Any one of them;

[0059] R is a single or multiple substituted functional group, wherein the functional group is any one of the following: a straight-chain alkyl group of C1-C24, a branched alkyl group of C1-C24, or an alkoxy group of C1-C24.

[0060] In some preferred embodiments, the derivative has the structure shown in formula (II), formula (III), or formula (IV):

[0061] , , ;

[0062] Wherein, R is a single or multiple substituted functional group, wherein the functional group is any one of the following: straight-chain alkyl, branched alkyl, and alkoxy groups of C1-C24.

[0063] In some preferred embodiments, the preparation method of the above-mentioned tetraazaisoindigo derivative specifically includes the following steps:

[0064] (1) Compound 1 and the brominating agent were placed in an organic solvent and stirred until clear to obtain compound 2;

[0065] (2) Under anhydrous and oxygen-free conditions, compound 2, trimethylethynylsilane, and catalyst were placed in an organic solvent and heated to 40-45℃ for 3-5 h. After separation and purification, compound 3 was obtained.

[0066] (3) Mix compound 3, an organic or inorganic base, and an organic solvent, and react at 60-80°C for 3-5 hours to obtain compound 4;

[0067] (4) Compound 4, RX1 and an inorganic base are reacted in an organic solvent, and after separation and purification, compound 5 is obtained; wherein X1 is a halogen atom and R is a single or multiple substituted functional group, wherein the functional group is any one of the following: straight-chain alkyl group of C1-C24, branched alkyl group of C1-C24, and alkoxy group of C1-C24.

[0068] (5) Under anhydrous and oxygen-free conditions, compound 5 is placed in an organic solvent with Ar1X2 or Ar2X2, a catalyst, and an inorganic base, and reacted at 90-110℃ for 20-24 h. After separation and purification, compound 6-1 or compound 6-2 is obtained; wherein Ar1 and Ar2 are both selected from , , , , , , , Any one of them; Ar1 ​​and Ar2 can be the same or different, and X2 is a borate group or a tin-containing group;

[0069] (6) Compound 6-1 or compound 6-2, aqueous tert-butanol and a brominating agent are mixed and stirred to obtain compound 7-1 or compound 7-2; wherein the water content of tert-butanol is 1% to 10%;

[0070] (7) Compound 7-1 and silver nitrate were mixed with solvent in a molar ratio of 1:(2-15) and stirred to obtain compound 8; Compound 7-2 and zinc powder were mixed with solvent in a molar ratio of 1:(5-20) and stirred to obtain compound 9;

[0071] (8) Compound 8, compound 9 and p-toluenesulfonic acid were refluxed in acetic acid to obtain compound 10, which is a tetraazaisoindigo derivative.

[0072] The reaction synthesis route is shown below:

[0073]

[0074] In some preferred embodiments, the brominating agent used in steps (1) and (6) is at least one of NBS, dibromohydantoin, bromine water, and hydrobromic acid.

[0075] In some preferred embodiments, in step (3), the organic base is at least one of sodium tert-butoxide, potassium tert-butoxide, and sodium ethoxide; and the inorganic base is at least one of potassium hydroxide and sodium hydroxide.

[0076] In some preferred embodiments, in step (4), the inorganic base is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydride, and potassium hydride.

[0077] In some preferred embodiments, the catalyst used in steps (2) and (5) is a palladium catalyst, for example, at least one of tetra(triphenylphosphine)palladium, tris(tri-p-methylphenylphosphine)palladium, tris(dibenzylideneacetone)palladium, bis(1,4-biphenylphosphine)butylpalladium dichloride, palladium acetate, and bis(triphenylphosphine)palladium dichloride.

[0078] In some preferred embodiments, the organic solvent in step (1) is selected from at least one of tetrahydrofuran, dichloromethane and trichloromethane; the organic solvent in step (2) is a mixture of amine solution and tetrahydrofuran, wherein the amine solution is selected from at least one of triethylamine, ethylenediamine and diisopropylamine; the organic solvents in steps (4) and (5) are selected from at least one of toluene, N,N-dimethylformamide, 1,2-dichloroethane, tetrahydrofuran, acetic acid and 1,4-dioxane; the solvent used in step (7) to prepare compound 8 is a mixture of 1,4-dioxane and water, and the solvent used to prepare compound 9 is acetic acid.

[0079] This invention provides a novel conjugated tetraazaisoindigo derivative with good solubility and simple synthesis method. Compared with other isoindigo semiconductor materials, tetraazaisoindigo has the advantage of being more electron-deficient, having a higher electron transport capacity, and having a higher yield.

[0080] The present invention will be further described in detail below through specific embodiments.

[0081] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the experimental materials and reagents used in the following examples are all available through conventional commercial channels.

[0082] Example 1

[0083] A tetraazaisoindigo derivative has the following structural formula:

[0084] ,in, .

[0085] The specific preparation method is as follows:

[0086]

[0087] (1) Synthesis of compound 2a

[0088] Compound 1a (7.7 g, 0.06 mol) was weighed into a dry 250 mL single-necked flask. After dissolving in 100 mL of THF, NBS (22.4 g, 0.126 mol) was slowly added to the flask. The reaction was stopped after stirring until the solution was clear. The remaining unreacted NBS was removed by diatomaceous earth filtration. The solvent in the system was then removed by rotary evaporation. The solution was purified by silica gel chromatography to obtain compound 2a in 40% yield.

[0089] (2) Synthesis of compound 3a

[0090] Under anhydrous and oxygen-free conditions, compound 2a (4.57 g, 16 mmol), CuI (0.30 g, 1.6 mmol), triethylamine (6.5 mL), and Pd(PPh3)2Cl (1.12 g, 1.6 mmol) were sequentially placed into a dry flask. Dry THF (150 mL) was then added to dissolve the compounds completely. After bubbling with Ar for 30 min, trimethylethynylsilane (2.4 mL, 16 mmol) was added to the reaction mixture. The mixture was stirred at 40 °C for 4 h, and the liquid was collected by filtration under reduced pressure. Tetrahydrofuran and triethylamine were then removed by distillation under reduced pressure. The product was subsequently washed with DCM and H2O and dried under vacuum. The product was purified by column chromatography (elution: PE / EA = 80:1) to give a white solid compound 3a (3.51 g), in 81% yield.

[0091] (3) Synthesis of compound 4a

[0092] Compound 3a (0.89 g, 3.89 mmol) was weighed into a dry 50 mL single-necked flask, and t-BuONa (2.79 g, 20 mmol) and NMP (15 mL) were added. After dissolution, the mixture was transferred to an oil bath and heated to 70 °C for 4 h. The mixture was then extracted with water and ethyl acetate to give a light brown solid 4a (0.67 g), with a yield of 69%.

[0093] (4) Synthesis of compound 5a

[0094] Compound 4a (0.88 g, 3.89 mmol) was weighed into a dry 50 mL single-necked flask. After dissolving in DMF (20 mL), KOH (0.37 g, 20 mmol) was slowly added to the flask. After stirring for 10 min, 2-butyl-1-bromooctane (3.98 g, 15.6 mmol) was added. After 4 h, the reaction was completed. DMF was distilled off under reduced pressure using an oil pump. The mixture was then extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, filtered, and purified by column chromatography. The eluent was petroleum ether and ethyl acetate in a ratio of 15:1 to give a pale yellow liquid 5a (1.39 g), with a yield of 90%.

[0095] (5) Synthesis of compound 6a

[0096] Compound 5a (10.0 g, 77.2 mmol), phenylboronic acid (14.1 g, 115.8 mmol), triphenylphosphine (2.02 g, 7.72 mmol), and potassium carbonate (33.0 g, 0.239 mol) were weighed and added sequentially to a 250 mL dry double-necked flask. Dry toluene (100 mL) and anhydrous ethanol (10 mL) were then added. After deoxygenating by blowing Ar bubbles for 30 min, palladium acetate (0.86 g, 3.86 mmol) was added to the flask. The mixture was heated to reflux in an oil bath at 100 °C and reacted overnight. Toluene was distilled off under reduced pressure, and the mixture was then extracted with water and ethyl acetate. After drying and filtration with anhydrous sodium sulfate, the mixture was purified by column chromatography to obtain a colorless solid 6a (12.6 g) in 95% yield. 1 H NMR (400 MHz, CDCl3) δ 8.95 (s, 1H), 8.12(d, J = 7.8 Hz, 2H), 7.45 (ddd, J = 21.0, 14.7, 7.3 Hz, 4H), 6.69 (s, 1H), 4.21 (d, J = 6.8 Hz, 2H), 2.10 – 1.87(m, 1H), 1.30 (ddd, J= 25.7, 19.0, 12.1 Hz, 17H), 0.92 – 0.75 (m, 6H). 13 C NMR (101 MHz, CDCl3) δ 145.02 (s), 140.91 (s), 138.29 (s), 138.02 (s), 136.08 (s), 133.00 (s), 128.75 (d, J = 13.4 Hz), 127.93 (s), 126.82 (s), 100.48 (s), 48.41 (s), 38.94 (s), 31.83 (s), 31.57 (s), 31.27 (s), 29.61 (s), 28.61 (s), 26.36 (s), 22.96 (s), 22.65 (s), 14.07 (d, J = 5.4 Hz). HRMS(ESI, m / z) calcd.for C 24 H 33 N3[M + H] + : 364.2764, found 364.2787.

[0097] (6) Synthesis of compound 7a

[0098] Weigh compound 6a (6.76 g, 18.6 mmol) into a dry 50 mL single-necked flask, and add tert-butanol containing water. t -BuOH (V t-BuOH =38 mL, H2O =2 mL), dissolved, then NBS (10.57 g, 59.4 mmol) was added. After reacting for 10 min, tert-butanol was distilled off under reduced pressure, then extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, filtered, and purified by column chromatography to obtain colorless liquid 7a (7.47 g) with a yield of 75%. 1 H NMR (400 MHz, CDCl3) δ 8.73 (s, 1H), 8.02(d, J = 5.4 Hz, 2H), 7.50 (s, 3H), 3.82 (d, J = 6.9 Hz, 2H), 2.06 (d, J = 30.3 Hz, 1H), 1.32 (dd, J = 42.4, 25.4 Hz, 17H), 0.86 (dd, J= 14.2, 6.5 Hz, 6H). 13 C NMR(101 MHz, CDCl3) δ 169.58 (s), 162.37 (s), 159.98 (s), 151.89 (s), 142.52(s), 131.96 (s), 130.89 (s), 128.62 (s), 120.98 (s), 44.37 (s), 39.86 (s), 36.21 (s), 31.91 (s), 31.64 (s), 31.31 (s), 29.69 (s), 28.58 (s), 26.38 (s), 23.05 (s), 22.77 (s), 14.19 (d, J = 7.1 Hz). HRMS(ESI, m / z) calcd. forC 24 H 31 Br2N3O [M + H] + : 536.08, found 536.0919.

[0099] (7) Synthesis of compound 8a

[0100] Weigh compound 7a (3.39 g, 6.30 mmol) into a dry 50 mL single-necked flask, and add solvent V. 1,4-dioxane =60 mL, V H2O =6 mL, dissolved, and then added excess silver nitrate (10.71 g, 63.0 mmol). After reacting for 2 h, the solid precipitate was removed by vacuum filtration, extracted with water and dichloromethane, dried with anhydrous sodium sulfate, filtered, and purified by column chromatography to obtain yellow solid 8a (2.31 g) with a yield of 90%. 1 H NMR (400 MHz, CDCl3) δ 8.93 (s, 1H), 8.14 (d, J =7.4 Hz, 2H), 7.67 - 7.44 (m, 3H), 3.80 (t, J = 16.3 Hz, 2H), 1.96 (d, J = 64.2Hz, 1H), 1.59 - 1.04 (m, 17H), 0.99 - 0.73 (m, 6H). 13C NMR (101 MHz, CDCl3) δ181.61 (s), 161.90 (s), 157.23 (s), 155.81 (s), 137.97 (s), 135.00 (s), 132.27 (s), 129.85 (s), 129.50 (s), 128.11 (s), 43.34 (s), 36.54 (s), 31.87 (d, J = 18.9 Hz), 31.46 (s), 29.74 (s), 28.70 (s), 26.47 (s), 23.11 (s), 22.75(s), 14.19 (s). HRMS(ESI, m / z) calcd. for C 24 H 31 N3O2[M + H]: 394.24, found394.2509.

[0101] (8) Synthesis of compound 9a

[0102] Compound 7a (3.80 g, 7.08 mmol) was weighed into a dry 50 mL single-necked flask, and CH3COOH (20 mL) was added to dissolve it. After dissolving, excess zinc powder (2.31 g, 35.4 mmol) was added. After reacting for 30 min, the solid precipitate was removed by vacuum filtration, extracted with water and dichloromethane, dried over anhydrous sodium sulfate, filtered, and purified by column chromatography to obtain a pale yellow liquid 9a (2.03 g) in 72% yield. 1 H NMR (400 MHz, CDCl3) δ 8.94 (s, 1H), 8.12 (d, J = 7.5 Hz, 2H), 7.45 (ddd, J = 23.3, 14.6, 7.4 Hz, 4H), 6.69 (d, J = 2.0 Hz, 1H), 4.22 (d, J =6.8 Hz, 2H), 2.08 – 1.96 (m, 1H), 1.30 (ddd, J = 26.1, 19.3, 12.2 Hz, 16H),0.85 (dd, J = 13.3, 6.9 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 145.02 (s), 140.89 (s), 138.26 (s), 138.01 (s), 136.09 (s), 133.03 (s), 128.77 (d, J = 13.4 Hz),126.83 (s), 100.46 (s), 48.41 (s), 38.95 (s), 31.84 (s), 31.54 (s), 31.25(s), 29.62 (s), 28.61 (s), 26.36 (s), 22.98 (s), 22.66 (s), 14.14 (t, J = 8.1Hz). HRMS(ESI, m / z) calcd. for C 24 H 33 N3O [M + H]: 380.26, found 380.2731.

[0103] (9) Synthesis of compound 10a

[0104] Compounds 8a (1.00 g, 2.54 mmol) and 9a (0.964 mg, 2.54 mmol) were weighed into a dry 50 mL two-necked flask. CH3COOH (20 mL) was added as solvent, and after dissolution, TsOH•H2O (0.964 mg, 2.54 mmol) was added. The mixture was transferred to a 60°C oil bath and reacted overnight. The mixture was then extracted with water and dichloromethane, dried over anhydrous sodium sulfate, filtered, and purified by column chromatography to give a blue solid 10a (1.5 g). Yield: 72%. Figures 1-2 As shown: 1 H NMR (400 MHz, CDCl3) δ8.94 (s, 1H), 8.13 (d, J = 3.4 Hz, 2H), 7.52 (s, 3H), 3.88 (d, J = 6.6 Hz, 2H), 2.13 (s, 1H), 1.52 – 1.09 (m, 16H), 0.85 (dt, J = 13.1, 6.5 Hz, 6H). 13 C NMR (101MHz, CDCl3) δ 169.01 (s), 161.64 (s), 155.47 (s), 150.75 (s), 135.69 (d, J=71.8 Hz), 135.23 – 134.96 (m), 132.71 (s), 131.09 (s), 129.26 (s), 127.50(s), 43.62 (s), 36.52 (s), 32.02 (s), 31.82 (s), 31.49 (s), 29.83 (s), 28.78(s), 26.49 (s), 23.17 (s), 22.77 (s), 14.23 (d, J = 2.9 Hz). HRMS(ESI, m / z)calcd. for C 48 H 62 N6O2[M + H]: 755.5012, found 755.4974.

[0105] Example 2

[0106] A tetraazaisoindigo derivative has the following structural formula:

[0107] ,in, .

[0108] The specific preparation method is as follows:

[0109] .

[0110] (1) Synthesis of compound 2b

[0111] Compound 1b (7.7 g, 0.06 mol) was weighed into a dry 250 mL single-necked flask. After dissolving in 100 mL of THF, NBS (22.4 g, 0.126 mol) was slowly added to the flask. The reaction was stopped after stirring until the solution was clear. The remaining unreacted NBS was removed by diatomaceous earth filtration. The solvent in the system was then removed by rotary evaporation. Compound 2b was obtained by silica gel chromatography with a yield of 60%.

[0112] (2) Synthesis of compound 3b

[0113] Under anhydrous and oxygen-free conditions, compound 2b (35.24 g, 169.0 mmol), CuI (3.22 g, 16.9 mmol), triethylamine (70.5 mL, 0.507 mol), and Pd(PPh3)2Cl2 (11.8 g, 16.9 mmol) were sequentially placed into a dry flask. Dry THF (150 mL) was then added to dissolve the compounds completely. After bubbling with Ar for 30 min, trimethylethylacetylenic silicon (31.6 mL, 0.219 mol) was added to the reaction mixture. The mixture was stirred at 40 °C for 4 h, and the liquid was collected by filtration under reduced pressure. Tetrahydrofuran and triethylamine were removed by vacuum distillation. The product was then washed with DCM and H2O and dried under vacuum. The product was purified by column chromatography (elution: PE / EA = 80:1) to give a white solid compound 3b (28.8 g) in 78% yield. 1 H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H), 5.65 (s, 2H), 0.27 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 164.39 (s), 159.72 (s), 159.22 (s), 106.17 (s), 101.10 (s), 95.57 (s), 0.14 (d, J = 28.2 Hz). HRMS(ESI, m / z) calcd. for C9H 12 ClN3Si [M + H]:226.0567, found 226.0573.

[0114] (3) Synthesis of compound 4b

[0115] Compound 3b (1.45 g, 6.42 mmol) was weighed into a dry 50 mL single-necked flask, and t-BuONa (1.23 g, 12.8 mmol) and NMP (15 mL) were added. After dissolution, the mixture was transferred to an oil bath and heated to 70°C for 4 h. The mixture was then extracted with water and ethyl acetate to give a light brown solid 4b (0.67 g), with a yield of 69%. 1 H NMR (400 MHz, DMSO) δ 12.48 (s, 1H), 9.03 (s, 1H), 7.73 (s, 1H), 6.75 (s, 1H). 13C NMR (101 MHz, DMSO) δ153.11 (s), 152.56 (s), 151.49 (s), 128.86 (s), 117.83 (s), 100.46 (s). HRMS(ESI, m / z) calcd. for C6H4ClN3[M + H]: 154.01, found 154.0188.

[0116] (4) Synthesis of compound 5b

[0117] Compound 4b (2.00 g, 13.0 mmol) was weighed into a dry 50 mL single-necked flask. After dissolving in DMF (20 mL), NaH (0.468 g, 19.5 mmol) was slowly added to the flask. After stirring for 10 min, 2-butyl-1-bromooctane (3.98 g, 15.6 mmol) was added. After 4 h, the reaction was completed. DMF was distilled off under reduced pressure using an oil pump, and the mixture was extracted with water and ethyl acetate. After drying with anhydrous sodium sulfate and filtering, the mixture was purified by column chromatography to obtain a pale yellow liquid 5b (3.6 g) with a yield of 90%. 1 H NMR (400MHz, CDCl3) δ 8.75 (s, 1H), 7.15 (s, 1H), 6.52 (s, 1H), 4.10 (d, J = 7.1 Hz,2H), 1.91 (s, 1H), 1.25 (dd, J = 37.5, 5.8 Hz, 17H), 0.83 (t, J = 6.3 Hz, 6H). 13 CNMR (101 MHz, CDCl3) δ 153.40 (s), 152.34 (s), 150.72 (s), 129.99 (s), 117.46 (s), 99.79 (s), 48.26 (s), 38.72 (s), 31.71 (s), 31.26 (s), 30.96 (s), 29.51(s), 28.41 (s), 26.17 (s), 22.90 (s), 22.58 (s), 14.00 (d, J = 9.3 Hz). HRMS(ESI, m / z) calcd. for C 18 H 28 ClN3[M + H]: 322.2050, found 322.2152.

[0118] (5) Synthesis of compound 6b

[0119] Compound 5b (2.00 g, 6.21 mmol) was weighed and placed into a 35 mL dry pressure-resistant tube. Dry toluene (30 mL) was added to dissolve the compound, and Ar bubbles were bubbled to remove oxygen for 30 min. Then Pd(PPh3)4 (0.86 g, 0.74 mmol) was added, followed by the addition of trimethyl(thiophene-2-yl)tin (2.8 mL, 7.46 mmol) using a syringe. After reacting overnight, toluene was distilled off under reduced pressure, and the mixture was extracted with water and ethyl acetate. After drying with anhydrous sodium sulfate and filtering, the mixture was purified by column chromatography to obtain a colorless liquid 6b (2.0 g) in 88% yield. 1 HNMR (400 MHz, CDCl3) δ 8.91 (s, 1H), 8.00 (s, 1H), 7.39 (d, J = 4.9 Hz, 1H), 7.13 (d, J = 2.6 Hz, 2H), 6.49 (s, 1H), 4.17 (d, J = 6.7 Hz, 2H), 1.99 (dd, J =11.6, 5.7 Hz, 1H), 1.42 – 1.17 (m, 17H), 0.85 (dd, J = 13.1, 6.9 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 154.50 (s), 151.35 (s), 149.31 (s), 145.03 (s), 129.96 (s), 129.61 (s), 127.97 (d, J = 4.0 Hz), 127.07 (s), 116.80 (s), 99.80 (s), 99.59 (s), 48.16 (d, J = 23.9 Hz), 38.81 (d, J = 14.5 Hz), 31.91 – 31.41 (m), 31.22 (s), 30.99 (s), 28.49 (d, J = 11.2 Hz), 27.86 (s), 26.86 (s), 22.94 (s), 22.64 (s), 14.06 (d, J = 5.4 Hz), 13.61 (s). HRMS(ESI, m / z) calcd. for C 22H 31 N3S[M + H]: 370.2317, found 370.2423.

[0120] (6) Synthesis of compound 7b

[0121] Weigh compound 6b (1.32 g, 3.59 mmol) into a dry 50 mL single-necked flask, and add tert-butanol (V) containing water. t-BuOH =16 mL, H2O =0.8 mL) were dissolved and NBS (2.04 g, 11.5 mmol) was added. After reacting for 10 min, tert-butanol was distilled off under reduced pressure, and the mixture was extracted with water and ethyl acetate. After drying with anhydrous sodium sulfate and filtering, the mixture was purified by column chromatography to obtain a colorless liquid 7b (1.5 g) with a yield of 78%. 1 H NMR (400 MHz, CDCl3) δ 8.60 (s, 1H), 8.04 (s, 1H), 7.55 (d, J = 4.6 Hz, 1H), 7.16 (s, 1H), 3.77 (d, J = 7.1 Hz, 2H), 2.08 (s, 1H), 1.34 (dd, J = 45.5, 15.9 Hz, 17H), 0.86 (dt, J = 12.2, 6.1 Hz, 6H). 13 C NMR (101MHz, CDCl3) δ 169.45 (s), 162.25 (s), 159.86 (s), 151.77 (s), 142.40 (s), 131.84 (s), 130.77 (s), 128.50 (s), 120.86 (s), 44.25 (s), 39.73 (s), 36.09(s), 31.79 (s), 31.52 (s), 31.19 (s), 29.57 (s), 28.46 (s), 26.26 (s), 22.93(s), 22.64 (s), 14.07 (d, J = 7.1 Hz). HRMS(ESI, m / z) calcd. for C 22 H 29 Br2N3OS [M + H]: 542.0476, found 542.0533.

[0122] (7) Synthesis of compound 8b

[0123] Weigh compound 7b (0.123 g, 0.221 mmol) into a dry 50 mL single-necked flask, and add solvent V. 1,4-dioxane =10 mL, V H2O =1 mL, dissolved, and then added excess silver nitrate (0.375 g, 2.21 mmol). After reacting for 2 h, the solid precipitate was removed by vacuum filtration, extracted with water and dichloromethane, dried with anhydrous sodium sulfate, filtered, and purified by column chromatography to obtain yellow solid 8b (80.3 mg) with a yield of 82%. 1 H NMR (400 MHz, CDCl3) δ 8.64 (d, J = 11.4 Hz, 1H),8.17 (s, 1H), 7.70 (d, J = 4.7 Hz, 1H), 7.23 (d, J = 4.3 Hz, 1H), 3.78 (d, J = 7.0Hz, 2H), 1.96 (d, J = 43.4 Hz, 1H), 1.64 – 1.06 (m, 17H), 1.00 – 0.75 (m, 6H). 13 C NMR (101 MHz, CDCl3) δ 178.48 (s), 170.22 (s), 165.98 (s), 159.00 (s), 151.83 (s), 142.47 (s), 134.67 (s), 133.21 (s), 129.09 (s), 107.01 (s), 43.73(s), 36.48 (s), 31.83 (s), 31.57 (s), 31.25 (s), 29.61 (s), 28.48 (s), 26.30(s), 22.98 (s), 22.65 (s), 14.07 (d, J = 2.8 Hz), -0.00 (s). HRMS(ESI, m / z)calcd. for C 22 H 29 N3O2S [M + H]: 400.20, found 400.2077.

[0124] (8) Synthesis of compound 9b

[0125] Compound 7b (0.150 g, 0.280 mmol) was weighed into a dry 50 mL single-necked flask, and CH3COOH (5 mL) solvent was added to dissolve it. After dissolving, excess zinc powder (29.2 g, 1.40 mmol) was added. After reacting for 30 min, the solid precipitate was removed by vacuum filtration, extracted with water and dichloromethane, dried over anhydrous sodium sulfate, filtered, and purified by column chromatography to obtain a pale yellow liquid 9b (80.3 mg) in 72% yield. 1 H NMR (400 MHz, CDCl3) δ 8.27 (s, 1H), 7.99 (s, 1H), 7.47(d, J = 4.6 Hz, 1H), 7.13 (s, 1H), 3.72 (d, J = 7.1 Hz, 2H), 3.57 (s, 2H), 2.02(s, 1H), 1.61 – 1.04 (m, 17H), 0.98 – 0.76 (m, 6H). 13 C NMR (101 MHz, CDCl3) δ174.35 (s), 165.51 (s), 160.32 (s), 148.62 (s), 143.18 (s), 129.92 (s), 129.06 (s), 128.15 (s), 113.59 (s), 43.61 (s), 36.19 (s), 32.78 (s), 31.85(s), 31.60 (s), 31.26 (s), 29.66 (s), 28.51 (s), 26.32 (s), 23.01 (s), 22.66(s), 14.08 (d, J = 3.3 Hz), -0.00 (s). HRMS(ESI, m / z) calcd. for C 22 H 31 N3OS [M + H]: 386.2266, found 386.2382.

[0126] (9) Synthesis of compound 10b

[0127] Compounds 8b (0.93 mg, 0.21 mmol) and 9b (0.94 mg, 0.21 mmol) were weighed into a dry 25 mL double-necked flask. CH3COOH (13 mL) was added as solvent, and after dissolution, TsOH•H2O (5.36 mg, 0.028 mmol) was added. The reaction was allowed to proceed overnight, followed by extraction with water and dichloromethane. The mixture was dried over anhydrous sodium sulfate, filtered, and purified by column chromatography to give an orange-red solid 10b (2.03 g). Yield: 72%. Figures 3-4 As shown: 1 H NMR (400 MHz, CDCl3) δ 10.11 (s,1H), 8.06 (s, 1H), 7.54 (d, J = 4.6 Hz, 1H), 7.15 (s, 1H), 3.84 (d, J = 6.9 Hz, 2H), 2.05 (s, 1H), 1.54 – 1.06 (m, 17H), 1.03 – 0.73 (m, 6H). 13 C NMR (101 MHz, CDCl3) δ 167.97 (s), 163.92 (s), 161.31 (s), 155.50 (s), 143.52 (s), 131.83 (s), 130.69 (s), 128.50 (s), 127.34 (s), 111.56 (s), 99.99 (s), 43.54 (s), 36.53 (s), 31.87 (s), 31.66 (s), 31.32 (s), 29.67 (s), 28.52 (s), 26.35 (s), 23.02 (s), 22.67 (s), 14.10 (s). HRMS(ESI, m / z) calcd. for C 44 H 58 N6O2S2[M + H]:767.4131, found 767.4134.

[0128] Example 3

[0129] A tetraazaisoindigo derivative is prepared as follows:

[0130] Compound 8c and its synthesis method are basically the same as those of compound 8a in Example 1, except that Ar1 is... .

[0131] Compound 8c (0.93 mg, 0.21 mmol) and compound 9b (0.94 mg, 0.21 mmol) were weighed into a dry 25 mL two-necked flask. CH3COOH (13 mL) was added as solvent, and after dissolution, TsOH•H2O (5.36 mg, 0.028 mmol) was added. The reaction was allowed to proceed overnight, followed by extraction with water and dichloromethane. The mixture was dried over anhydrous sodium sulfate, filtered, and purified by column chromatography to give a purple solid 10c (1.93 g). Yield: 70%. Figures 5-6 As shown: 1 H NMR (400 MHz, CDCl3) δ 10.08 (d, J =17.2 Hz, 1H), 8.71 (s, 1H), 8.09 (s, 1H), 7.58 (d, J = 3.9 Hz, 1H), 7.47 (s,1H), 7.17 (s, 1H), 7.11 (s, 1H), 3.82 (t, J = 6.5 Hz, 4H), 2.06 (d, J = 37.9 Hz, 2H), 1.31 (dd, J = 51.1, 27.2 Hz, 35H), 0.86 (d, J = 5.6 Hz, 13H). 13 C NMR (101MHz, CDCl3) δ 166.86 (s), 166.20 (s), 164.86 (s), 161.95 (s), 156.08 (s), 153.60 (s), 145.34 (s), 143.50 (d, J = 4.7 Hz), 134.71 (s), 133.39 (s), 132.34(s), 131.76 (s), 131.14 (s), 130.57 (s), 128.63 (s), 128.21 (s), 127.12 (s), 118.36 (s), 111.64 (s), 77.30 (d, J = 11.5 Hz), 77.04 (s), 76.72 (s), 43.82 (s), 43.30 (s), 36.41 (d, J = 14.6 Hz), 32.20 – 31.38 (m), 31.26 (s), 29.72(s), 28.56 (d, J= 4.6 Hz), 26.38 (d, J = 4.1 Hz), 23.06 (d, J = 2.3 Hz), 22.69 (d, J = 3.0 Hz), 14.13 (d, J = 2.4 Hz). HRMS(ESI, m / z) calcd. for C 44 H 59 BrN6OS2[M + H]:845.3246, found 845.3213.

[0132] Comparative Example 1

[0133]

[0134] Synthesis of compound Th-II

[0135] Weigh commercially available bromoisoindigo (0.10 g, 0.132 mmol) into a 35 mL dry pressure-resistant tube, add dry toluene (10 mL) to dissolve, and then purge with Ar bubbles for 30 min to remove oxygen. Then add Pd(PPh3)4 (0.036 g, 0.0264 mmol) to the flask, and then add trimethyl(thiophene-2-yl)tin (0.11 g, 0.29 mmol) using a syringe. React overnight, distill off the toluene under reduced pressure, extract with water and ethyl acetate, dry with anhydrous sodium sulfate, filter, and purify by column chromatography to obtain a colorless liquid Th-II (0.06 g) with a yield of 60%.

[0136] Performance testing

[0137] Optical and electrochemical measurements and OFET device performance tests were performed on compound 10a (Ph-PyrII) in Example 1, compound 10b (Th-PymII) in Example 2, compound 10c (Th-PyrPymII) in Example 3, and compound Th-II in Comparative Example 1.

[0138] Optical testing: Using dichloromethane as solvent and compounds 10a, 10b, 10c and Th-II as solutes, 10... -5 5 mL of a mol / L sample solution was used to test the absorption spectrum of the compound using a UV-Vis absorption spectrometer.

[0139] Results analysis: such as Figure 7 As shown in (a), the wavelength of the compound in DCM can be determined by plotting the tangent to the absorption curve of the compound in DCM solution. The band gap of the compound can be estimated from the cutoff position of the maximum absorption peak in the ultraviolet spectrum. According to formula E...g =1240 / X can be used to calculate the optical band gap (relevant data are in Table 1). It can be seen that the absorption spectra of tetrazolium isoindigo and Th-II in diluted solutions exhibit dual-band absorption characteristics. Compared to the absorption spectrum of Th-II (550 nm), Ph-PyrII shows a significant red-shifted maximum absorption peak (583 nm), which corresponds to the HOMO-LUMO transition, indicating its smaller optical band gap. On the other hand, Th-PymII shows a significant blue-shifted maximum absorption peak (505 nm) and exhibits obvious... 0-0 and 0-1 The oscillating peaks indicate that Th-PymII may have a more rigid planar skeletal structure compared to Ph-PyrII, while the spectral characteristics of Th-PyrPymII are similar to those of Ph-PyrII. Since Th-PymII emits strong fluorescence at 365 nm excitation in both solution and solid states, while Th-II, Ph-PyrII, and Th-PyrPymII do not fluoresce, the four compounds were compared in DCM solution (all at a concentration of 10). -5 The emission spectrum of the sample (mol / L) was excited using the maximum absorption wavelength in the low-energy region, and the results are as follows: Figure 7 As shown in (b) above, Th-PymII exhibits a strong emission peak at 620 nm, Th-PyrPymII has a weaker emission peak at 710 nm, while Ph-PyrII and Th-II show no distinguishable emission peaks. The fluorescence quantum yield of these four compounds was detected using steady-state fluorescence spectroscopy, revealing that Th-PymII... F F The fluorescence quantum yield was 39.87%, while the other three compounds were undetectable. The completely different fluorescence quantum yields of Th-PymII, Ph-PyrII, and Th-PyrPymII indicate that the position of the nitrogen atom has a significant impact on the photophysical properties of these three isomers.

[0140] Electrochemical testing: Compounds 10a–10c were tested using cyclic voltammetry (CV) on a standard commercial electrochemical analyzer (Shanghai Chenhua Instrument Co., Ltd., CHI520E). The three-electrode system consisted of a cylindrical platinum working electrode, a platinum wire counter electrode, and an Ag / AgCl reference electrode. The potential of the Ag / AgCl reference electrode was internally calibrated based on ferrocene. 0.1M tetrabutylammonium hexafluorophosphate (TBAPF6) solutions in deoxydichloromethane and deoxytetrahydrofuran were prepared as electrolyte solutions. After adding the sample to the electrolyte solutions, the samples were placed in dried containers and plugged with three-hole stoppers. The working electrode, reference electrode, and counter electrode were connected with wires and inserted into the three-hole stoppers, and argon gas was purged to remove air. The test was then started, with the range set to 0–2.0 V. Oxidation and reduction curves for all solvents were measured.

[0141] Results Analysis: The redox peak positions of the compounds were calibrated using the ferrocene / ferrocene cation (Foc / Foc+) redox system as an internal standard. The LUMO and HOMO energy levels of the compounds were estimated from the initial reduction and oxidation peak potentials. The HOMO and LUMO energy levels of the three isomers were determined by cyclic voltammetry. Figure 8 Cyclic voltammetry (vs. Ag / AgCl) of Ph-PyrII, Th-PyrPymII, and Th-PymII in DCM is shown at a scan rate of 0.1 V / s. Relevant data are recorded in Table 1. HOMO and LUMO levels are expressed as absolute values. It can be seen that the LUMO levels of Ph-PyrII (-4.13 eV) and Th-PyrPymII (-4.07 eV) are lower than those of Th-PymII (-3.91 eV), indicating a higher degree of electron deficiency for Ph-PyrII and Th-PyrPymII. The LUMO levels of both symmetric and asymmetric tetraazaisoindigo are lower than those of Th-II (-3.65 eV).

[0142] Table 1. Optical and electrochemical properties of tetraazine indigo

[0143]

[0144] OFET performance testing: OFET devices were fabricated using Th-PymII, Th-PyrPymII, and Ph-PyrII as active layers, respectively. Device performance was tested in a glove box. The electrical characteristics of the OFETs were analyzed using a Keithley 4200 SCS semiconductor parameter analyzer, and the results are recorded in Table 2.

[0145] Table 2. OFET characteristics of tetraazaisoindigo

[0146]

[0147] As shown in Table 2, the Th-PymII device exhibits pure n-type transport characteristics, with the highest electron mobility reaching 0.11 cm⁻¹. 2 V -1 S -1 The operating voltage is relatively small (V) th 11 V), with a switching ratio as high as 10. 5 For Ph-PyrII, a BG / BC structure was selected. Ph-PyrII was spin-coated onto a dielectric layer with pre-deposited gold source / drain electrodes, and the OFET performance was measured after solvent evaporation. The device exhibited excellent balanced polarity transport characteristics, with maximum hole and electron mobilities of 0.29 and 0.24 cm⁻¹, respectively. 2 V -1 s -1 It exhibits almost no hysteresis and a high on / off ratio. Although the LUMO level (-4.13 eV) of Ph-PyrII is lower than that of Th-PymII, its narrower E0... gap This determines its balanced bipolar transport characteristics. Th-PyrPymII is used to fabricate BG / BCOFET devices via spin-coating deposition. Because Th-PyrPymII has a similar LUMO energy level and E0 to Ph-PyrII, it is suitable for applications where Th-PyrPymII has a similar energy level to Ph-PyrII. gap Therefore, it also has the maximum hole and electron mobility of 0.09 cm⁻¹. 2 V -1 S -1 Its bipolar transmission characteristics.

[0148] It should be noted that all the above embodiments belong to the same inventive concept, and the descriptions of each embodiment have different focuses. Where the description in a particular embodiment is not detailed, please refer to the description in other embodiments.

[0149] The embodiments described above are merely illustrative of implementation methods of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A tetraazaisoindigo derivative, characterized in that, Its structural formula is shown in equation (Ⅰ): ， Where X is N and Y is C or X is C and Y is N; Ar1 is selected from , , , , , , , Any one of them; Ar2 is selected from , , , , , , , Any one of them; R is a single or multiple substituted functional group, wherein the functional group is any one of the following: a straight-chain alkyl group of C1-C24, a branched alkyl group of C1-C24, or an alkoxy group of C1-C24.

2. The tetraazaisoindigo derivative according to claim 1, characterized in that, It has the structure shown in equation (II), equation (III), or equation (IV): 、 ； Wherein, R is a single or multiple substituted functional group, wherein the functional group is any one of the following: straight-chain alkyl, branched alkyl, and alkoxy groups of C1-C24.

3. A method for preparing a tetraazaisoindigo derivative as described in any one of claims 1 to 2, characterized in that, Includes the following steps: (1) Compound 1 was subjected to bromination to obtain compound 2; (2) Compound 2 was catalytically coupled with trimethylethynylsilane to obtain compound 3; (3) Compound 3 was subjected to a cyclization reaction under organic or inorganic base conditions to obtain compound 4; (4) Compound 4 and RX1 were subjected to alkylation under inorganic base conditions to obtain compound 5; (5) Compound 5 is coupled with Ar1X2 or Ar2X2 under palladium catalysis to obtain compound 6-1 or compound 6-2; (6) Reacting compound 6-1 or compound 6-2 with a bromine reagent in aqueous tert-butanol to obtain compound 7-1 or compound 7-2; (7) Compound 7-1 was oxidized to obtain compound 8, and compound 7-2 was reduced to obtain compound 9; (8) Compound 8 and compound 9 were refluxed under acidic conditions to obtain compound 10, which is the tetraazaisoindigo derivative; The reaction synthesis route is shown below: Where X is N and Y is C or X is C and Y is N; X1 is a halogen atom, and X2 is a borate group or a tin-containing group; Ar1 is selected from , , , , , , , Any one of them; Ar2 is selected from , , , , , , , Any one of them; R is a single or multiple substituted functional group, wherein the functional group is any one of the following: a straight-chain alkyl group of C1-C24, a branched alkyl group of C1-C24, or an alkoxy group of C1-C24.

4. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In step (1), the brominating reagent used in the bromination reaction is at least one of NBS, dibromohydantoin, bromine water, and hydrobromic acid.

5. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In step (3), the organic base is at least one of sodium tert-butoxide, potassium tert-butoxide, and sodium ethoxide; the inorganic base is at least one of potassium hydroxide and sodium hydroxide.

6. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In step (4), the inorganic base is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydride, and potassium hydride.

7. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In steps (2) and (5), the catalyst used in the coupling reaction is at least one of tetra(triphenylphosphine)palladium, tris(tri-p-methylphenylphosphine)palladium, tris(dibenzylideneacetone)palladium, bis(1,4-biphenylphosphine)butylpalladium dichloride, palladium acetate, and bis(triphenylphosphine)palladium dichloride.

8. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In step (6), the water content of the tert-butanol is 1% to 10%; the brominating agent is at least one of NBS, dibromohydantoin, bromine water, and hydrobromic acid.

9. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In step (7), compound 7-1 is oxidized to obtain compound 8. The oxidant used is silver nitrate, and the molar ratio of compound 7-1 to silver nitrate is 1:(2~15). Compound 7-2 was reduced to obtain compound 9. The reducing agent used was zinc powder, and the molar ratio of compound 7-2 to zinc powder was 1:(5~20).

10. The method for preparing the tetraazaisoindigo derivative according to claim 3, characterized in that, In step (8), compounds 8, 9 and p-toluenesulfonic acid are refluxed in acetic acid to obtain the tetraazaisoindigo derivative.

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