Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof

Abstract

The invention belongs to the field of optoelectronic materials and discloses an organic semiconductor material containing metalloporphyrin-triphenylamine and a preparation method and application thereof. The organic semiconductor material containing metalloporphyrin-triphenylamine has a structural formula (I) shown in the specification, wherein in the formula, n is an integer from 1 to 100; R1, R2, R3 and R4 are H, C1-C32 alkyl, phenyl and alkylbenzene or alkoxy benzene containing one or more C1-C32; and M is a metal ion. The organic semiconductor material containing metalloporphyrin-triphenylamine has a wide light absorption range, thus improving the sunlight use ratio of the material. The material also has better heat stability and environmental stability. Besides, the preparation method is simple in process and easy to operate and control.

Description

technical field

[0001] The invention relates to an organic semiconductor material, in particular to a metal porphyrin-triphenylamine-containing organic semiconductor material.

[0002] The invention also relates to a preparation method and application of the metal porphyrin-triphenylamine-containing organic semiconductor material. Background technique

[0003] The preparation of low-cost and high-efficiency solar cells using cheap materials has always been a research hotspot and difficulty in the field of photovoltaics. Due to the complex production process and high cost of silicon cells currently used on the ground, their application is limited. In order to reduce the cost of batteries and expand the application range, people have been looking for new solar cell materials for a long time. Organic semiconductor materials have attracted much attention due to the advantages of readily available raw materials, low cost, simple preparation process, good environmental stability...

Examples

preparation example Construction

[0040] The preparation method of the metal porphyrin-triphenylamine-containing organic semiconductor material designed in the present invention has the following steps: step S1, adding dibromotriphenylamine (Y) into the first organic solvent, cooling to -78°C, add n-BuLi dropwise, then react at -78°C for 0.5-5h, then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-di Xaborane (X) (the molar amount of which is 2 to 4 times the molar amount of dibromotriphenylamine (Y)), or the structural formula: The bispinacolate diboron) was reacted at -78°C for 0.5-5h, then naturally warmed to room temperature, and after 1-48h of reaction, 4,4'-bis(4,4,5,5-tetramethyl Base-1,3,2-dioxaborolane) triphenylamine (G); Wherein, the first organic solvent is at least one in anhydrous tetrahydrofuran, ether or dioxane, and the reaction formula is as follows:

[0041]

[0042]

[0043] Step S2, dissolving dipyrromethane (A), the first silafluorene derivative (B) and the second silafluorene derivati...

Embodiment 1

[0058] This embodiment discloses a 10,20-bis(9',9'-dioctyl)silafluorene zinc porphyrin-triphenylamine organic semiconductor material (n=40) with the following structure:

[0059]

[0060] The preparation steps of the above-mentioned organic semiconductor material are as follows:

[0061] 1. Synthesis of 4,4'-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) triphenylamine

[0062]

[0063] Under the protection of nitrogen, add p-4,4'-dibromotriphenylamine (8.0g, 0.02mol) into the three-necked flask, add 150ml of tetrahydrofuran solvent, and slowly inject n-butyl Lithium (16.8mL, 2.5M, 0.04mol), continue to stir the reaction for 2h, inject 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2 - Dioxaborolane (8.7 mL, 0.04 mol), stirred overnight at room temperature. Saturated aqueous sodium chloride (30ml) was added to terminate the reaction, extracted with chloroform, dried over anhydrous sodium sulfate, and filtered, the filtrate was collected and the solvent was evaporated off. Finally...

Embodiment 2

[0077] This embodiment discloses a 10-(9'-methyl-9'-hexadecyl)silafluorene-20-(9'-tridodecyl)silafluorene iron porphyrin-triphenylamine organic Semiconductor materials (n=56)

[0078]

[0079] The preparation steps of the above-mentioned organic semiconductor material are as follows:

[0080] 1. Synthesis of 4,4'-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) base triphenylamine

[0081] Its preparation sees embodiment 1 for details.

[0082] 2. Synthesis of 5-(9'-methyl-9'-hexadecyl)silafluorene-15-(9'-docosyl)silafluorene porphyrin

[0083]

[0084] Set up an anhydrous and oxygen-free device, weigh the intermediates 2-aldehyde-9-methyl-9-hexadecylsilafluorene (0.45g, 1mmol), 2-aldehyde-9-docosylsilafluorene ( 0.66g, 1mmol), dipyrromethane (0.30g, 2mmol), dissolved in 250ml of dichloromethane, blown nitrogen for 30min, added 2ml of trifluoroacetic acid into the syringe, stirred at 100°C for 1h, then added dichlorodicyanobenzene Quinone (DDQ) (1.8g, 8mmol), continue st...

technical field

[0001] The invention relates to an organic semiconductor material, in particular to a metal porphyrin-triphenylamine-containing organic semiconductor material.

[0002] The invention also relates to a preparation method and application of the metal porphyrin-triphenylamine-containing organic semiconductor material. Background technique

[0003] The preparation of low-cost and high-efficiency solar cells using cheap materials has always been a research hotspot and difficulty in the field of photovoltaics. Due to the complex production process and high cost of silicon cells currently used on the ground, their application is limited. In order to reduce the cost of batteries and expand the application range, people have been looking for new solar cell materials for a long time. Organic semiconductor materials have attracted much attention due to the advantages of readily available raw materials, low cost, simple preparation process, good environmental stability...

Examples

preparation example Construction

[0040] The preparation method of the metal porphyrin-triphenylamine-containing organic semiconductor material designed in the present invention has the following steps: step S1, adding dibromotriphenylamine (Y) into the first organic solvent, cooling to -78°C, add n-BuLi dropwise, then react at -78°C for 0.5-5h, then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-di Xaborane (X) (the molar amount of which is 2 to 4 times the molar amount of dibromotriphenylamine (Y)), or the structural formula: The bispinacolate diboron) was reacted at -78°C for 0.5-5h, then naturally warmed to room temperature, and after 1-48h of reaction, 4,4'-bis(4,4,5,5-tetramethyl Base-1,3,2-dioxaborolane) triphenylamine (G); Wherein, the first organic solvent is at least one in anhydrous tetrahydrofuran, ether or dioxane, and the reaction formula is as follows:

[0041]

[0042]

[0043] Step S2, dissolving dipyrromethane (A), the first silafluorene derivative (B) and the second silafluorene derivati...

Embodiment 1

[0058] This embodiment discloses a 10,20-bis(9',9'-dioctyl)silafluorene zinc porphyrin-triphenylamine organic semiconductor material (n=40) with the following structure:

[0059]

[0060] The preparation steps of the above-mentioned organic semiconductor material are as follows:

[0061] 1. Synthesis of 4,4'-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) triphenylamine

[0062]

[0063] Under the protection of nitrogen, add p-4,4'-dibromotriphenylamine (8.0g, 0.02mol) into the three-necked flask, add 150ml of tetrahydrofuran solvent, and slowly inject n-butyl Lithium (16.8mL, 2.5M, 0.04mol), continue to stir the reaction for 2h, inject 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2 - Dioxaborolane (8.7 mL, 0.04 mol), stirred overnight at room temperature. Saturated aqueous sodium chloride (30ml) was added to terminate the reaction, extracted with chloroform, dried over anhydrous sodium sulfate, and filtered, the filtrate was collected and the solvent was evaporated off. Finally...

Embodiment 2

[0077] This embodiment discloses a 10-(9'-methyl-9'-hexadecyl)silafluorene-20-(9'-tridodecyl)silafluorene iron porphyrin-triphenylamine organic Semiconductor materials (n=56)

[0078]

[0079] The preparation steps of the above-mentioned organic semiconductor material are as follows:

[0080] 1. Synthesis of 4,4'-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) base triphenylamine

[0081] Its preparation sees embodiment 1 for details.

[0082] 2. Synthesis of 5-(9'-methyl-9'-hexadecyl)silafluorene-15-(9'-docosyl)silafluorene porphyrin

[0083]

[0084] Set up an anhydrous and oxygen-free device, weigh the intermediates 2-aldehyde-9-methyl-9-hexadecylsilafluorene (0.45g, 1mmol), 2-aldehyde-9-docosylsilafluorene ( 0.66g, 1mmol), dipyrromethane (0.30g, 2mmol), dissolved in 250ml of dichloromethane, blown nitrogen for 30min, added 2ml of trifluoroacetic acid into the syringe, stirred at 100°C for 1h, then added dichlorodicyanobenzene Quinone (DDQ) (1.8g, 8mmol), continue st...

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