Donor-acceptor-donor-acceptor-donor oligothiophene derivative taking dithienopyrrole as molecular center and preparation method of derivative

Abstract

The invention provides a donor-acceptor-donor-acceptor-donor oligothiophene derivative taking dithienopyrrole as a molecular center. The chemical structural formula of the derivative is shown in formula I in the description, synthesis comprises the steps that 2,6-di(trimethyl-tin)-N-iso-octane-dithieno[3,2-b:2',3'-d]pyrrole and 4,7-dibromine-[1,2,5]thiadiazole[3,4-c]pyridine react to synthesize an intermediate (2,6-2{(4-(7-bromine-[1,2,5]thiadiazole[3,4-c]pyridine)}-N-iso-octane-dithieno[3,2-b:2',3'-d]pyrrole); and then the (2,6-2{(4-(7-bromine-[1,2,5]thiadiazole[3,4-c]pyridine)}-N-iso-octane-dithieno[3,2-b:2',3'-d]pyrrole) reacts with 2-(trimethyl-tin)-5-(4-n-hexylphenyl)thiophene to obtain the target oligothiophene derivative. The oligothiophene derivative has a narrow band gap, a lowHOMO energy level, good solubility and film formation, and is expected to be used as an organic semiconductor material in the preparation of organic thin film field effect transistors, organic light emitting diodes and organic solar cell devices.

Description

technical field

[0001] The invention belongs to the technical field of thiophene derivatives and organic semiconductor materials, in particular to donate-accept-donate-accept-donate oligomerized thiophene derivatives with dithienopyrrole as the molecular center and a preparation method thereof. Background technique

[0002] Among many organic semiconductor materials, oligothiophene and its derivatives have the advantages of simple synthesis, easy purification, high mobility, adjustable energy level and good stability, and have become the most important class in the preparation of organic semiconductor devices. donor material. However, oligothiophene and its derivatives with good semiconductor properties usually have poor solubility and film-forming properties, and are difficult to make devices, so that they are difficult to apply in practice. Therefore, how to improve the solubility and film-forming properties of polythiophene and its derivatives under the premise of ensuri...

Examples

Embodiment 1

[0033] 2,6-Di{(4-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine)}-N-isooctyldithieno[3,2- b: Synthesis of 2',3'-d]pyrrole:

[0034] Under nitrogen protection, 2,6-bis(trimethyltin)-N-isooctyldithieno[3,2-b:2',3'-d]pyrrole (5.56g, 9mmol), 4,7-Dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (2.65g, 9mmol) and tetrakis(triphenylphosphine)palladium (0.15g, 0.13mmol) were added to 500ml Into a three-neck round bottom flask, inject 150ml of dry N,N-dimethylformamide, and stir the reaction at 80°C for 60h; after the reaction, cool the reactant to room temperature, add deionized water, extract three times with dichloromethane, and combine organic phase; the organic phase was washed with anhydrous MgSO 4 Dry, filter and concentrate under reduced pressure to obtain a small amount of dark red solid; the product is purified by silica gel column chromatography, the eluent is a mixture of dichloromethane and n-hexane (volume ratio 1:1), and a purple-red solid is obtained. Solid 0.43 g, yield 15.1%...

Embodiment 2

[0038] 2,6-Di{(4-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine)}-N-isooctyldithieno[3,2- b: Synthesis of 2',3'-d]pyrrole:

[0039] Under argon protection, 2,6-bis(trimethyltin)-N-isooctyldithieno[3,2-b:2',3'-d]pyrrole (2.16g, 3.5mmol ), 4,7-dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (2.58g, 8.75mmol) and bis(triphenylphosphine)palladium dichloride (0.12g ,0.17mmol) into a 500ml three-necked round-bottomed flask, inject 150ml of dry N,N-dimethylformamide, stir and react at 100°C for 35h; Chloromethane was extracted three times, and the organic phase was combined; the organic phase was washed with anhydrous MgSO 4Dry, filter and concentrate under reduced pressure to obtain a small amount of dark red solid; the product is purified by silica gel column chromatography, the eluent is a mixture of dichloromethane and n-hexane (volume ratio 1:1), and a purple-red solid is obtained. Solid 1.0 g, yield 39.8%.

[0040] Synthesis of oligomers:

[0041] Under the protection of argon, the ...

Embodiment 3

[0043] 2,6-Di{(4-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine)}-N-isooctyldithieno[3,2- b: Synthesis of 2',3'-d]pyrrole:

[0044] Under the protection of helium, 2,6-bis(trimethyltin)-N-isooctyldithieno[3,2-b:2',3'-d]pyrrole (3.01g, 4.9mmol ), 4,7-dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (7.21g, 24.50mmol) and tris(dibenzylideneacetone)dipalladium (0.12g, 0.13mmol) into a 500ml three-necked round-bottomed flask, inject 150ml of dry N,N-dimethylformamide, stir and react at 130°C for 10h; Extracted three times with methane, combined the organic phase; the organic phase was washed with anhydrous MgSO 4 Dry, filter and concentrate under reduced pressure to obtain a small amount of dark red solid; the product is purified by silica gel column chromatography, the eluent is a mixture of dichloromethane and n-hexane (volume ratio 1:1), and a purple-red solid is obtained. Solid 1.04 g, yield 30.1%.

[0045] Synthesis of oligomers:

[0046] Under the protection of helium, the interme...

technical field

[0001] The invention belongs to the technical field of thiophene derivatives and organic semiconductor materials, in particular to donate-accept-donate-accept-donate oligomerized thiophene derivatives with dithienopyrrole as the molecular center and a preparation method thereof. Background technique

[0002] Among many organic semiconductor materials, oligothiophene and its derivatives have the advantages of simple synthesis, easy purification, high mobility, adjustable energy level and good stability, and have become the most important class in the preparation of organic semiconductor devices. donor material. However, oligothiophene and its derivatives with good semiconductor properties usually have poor solubility and film-forming properties, and are difficult to make devices, so that they are difficult to apply in practice. Therefore, how to improve the solubility and film-forming properties of polythiophene and its derivatives under the premise of ensuri...

Examples

Embodiment 1

[0033] 2,6-Di{(4-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine)}-N-isooctyldithieno[3,2- b: Synthesis of 2',3'-d]pyrrole:

[0034] Under nitrogen protection, 2,6-bis(trimethyltin)-N-isooctyldithieno[3,2-b:2',3'-d]pyrrole (5.56g, 9mmol), 4,7-Dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (2.65g, 9mmol) and tetrakis(triphenylphosphine)palladium (0.15g, 0.13mmol) were added to 500ml Into a three-neck round bottom flask, inject 150ml of dry N,N-dimethylformamide, and stir the reaction at 80°C for 60h; after the reaction, cool the reactant to room temperature, add deionized water, extract three times with dichloromethane, and combine organic phase; the organic phase was washed with anhydrous MgSO 4 Dry, filter and concentrate under reduced pressure to obtain a small amount of dark red solid; the product is purified by silica gel column chromatography, the eluent is a mixture of dichloromethane and n-hexane (volume ratio 1:1), and a purple-red solid is obtained. Solid 0.43 g, yield 15.1%...

Embodiment 2

[0038] 2,6-Di{(4-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine)}-N-isooctyldithieno[3,2- b: Synthesis of 2',3'-d]pyrrole:

[0039] Under argon protection, 2,6-bis(trimethyltin)-N-isooctyldithieno[3,2-b:2',3'-d]pyrrole (2.16g, 3.5mmol ), 4,7-dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (2.58g, 8.75mmol) and bis(triphenylphosphine)palladium dichloride (0.12g ,0.17mmol) into a 500ml three-necked round-bottomed flask, inject 150ml of dry N,N-dimethylformamide, stir and react at 100°C for 35h; Chloromethane was extracted three times, and the organic phase was combined; the organic phase was washed with anhydrous MgSO 4Dry, filter and concentrate under reduced pressure to obtain a small amount of dark red solid; the product is purified by silica gel column chromatography, the eluent is a mixture of dichloromethane and n-hexane (volume ratio 1:1), and a purple-red solid is obtained. Solid 1.0 g, yield 39.8%.

[0040] Synthesis of oligomers:

[0041] Under the protection of argon, the ...

Embodiment 3

[0043] 2,6-Di{(4-(7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine)}-N-isooctyldithieno[3,2- b: Synthesis of 2',3'-d]pyrrole:

[0044] Under the protection of helium, 2,6-bis(trimethyltin)-N-isooctyldithieno[3,2-b:2',3'-d]pyrrole (3.01g, 4.9mmol ), 4,7-dibromo-[1,2,5]thiadiazolo[3,4-c]pyridine (7.21g, 24.50mmol) and tris(dibenzylideneacetone)dipalladium (0.12g, 0.13mmol) into a 500ml three-necked round-bottomed flask, inject 150ml of dry N,N-dimethylformamide, stir and react at 130°C for 10h; Extracted three times with methane, combined the organic phase; the organic phase was washed with anhydrous MgSO 4 Dry, filter and concentrate under reduced pressure to obtain a small amount of dark red solid; the product is purified by silica gel column chromatography, the eluent is a mixture of dichloromethane and n-hexane (volume ratio 1:1), and a purple-red solid is obtained. Solid 1.04 g, yield 30.1%.

[0045] Synthesis of oligomers:

[0046] Under the protection of helium, the interme...

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