阅读说明：本技术 多稠环n型半导体材料的制备方法及其应用 (Preparation method and application of multi-condensed-ring n-type semiconductor material ) 是由 黎静 杨志伟 谭陆西 于 2021-04-19 设计创作，主要内容包括：本发明涉及一种超低LUMO能级的多SN杂稠环n型有机半导体材料,该材料可应用于有机场效应晶体管,有机薄膜太阳能电池及钙钛矿电池。以1,5-二氨基萘为初始原料,经多步合成,得到5,11-二氟喹喔啉[6,5-f]喹喔啉,再与1,1-二氰基乙烯-2,2-二硫醇钠反应,即得所述多稠环n型半导体材料。本发明所述材料由多个芳香环稠合而成,具有较大的平面结构,且四个强吸电子基团(氰基)能有效降低分子LUMO能级,是一种具有较好发展前景的n型半导体材料。(The invention relates to an ultra-low LUMO energy level multi-SN hetero-condensed ring n-type organic semiconductor material which can be applied to organic field effect transistors, organic thin-film solar cells and perovskite cells. 1, 5-diaminonaphthalene is used as an initial raw material, 5, 11-difluoroquinoxaline [6,5-f ] quinoxaline is obtained through multi-step synthesis, and then the 5, 11-difluoroquinoxaline [6,5-f ] quinoxaline reacts with 1, 1-dicyanoethylene-2, 2-sodium dithiolate, so that the multi-condensed-ring n-type semiconductor material is obtained. The material is formed by fusing a plurality of aromatic rings, has a larger plane structure, and four strong electron-withdrawing groups (cyano groups) can effectively reduce the LUMO energy level of molecules, thereby being an n-type semiconductor material with better development prospect.)

1. The poly-condensed-ring n-type semiconductor material is characterized in that the molecular structural formula of the material is shown as formula I:and the R is a solubilizing group.

2. The multiple fused ring n-type semiconductor material of claim 1, wherein R is triisopropylsilyl or 2-octylthiophene or n-octylphenyl ether.

3. The method for preparing a multiple condensed ring n-type semiconductor material according to claim 1, wherein the preparation steps are as follows:

(1) reacting the formula III with a diketone compound to obtain a compound of a formula II;

(2) reacting the compound shown in the formula II with 1, 1-dicyanoethylene-2, 2-sodium dithiolate to obtain the compound shown in the formula I.

4. The preparation method according to claim 3, wherein the reaction solvent in the step (1) is ethanol and acetic acid solution, the reaction temperature is 80 ℃, and the reaction time is 23 h.

5. The method according to claim 4, wherein the volume ratio of ethanol to acetic acid is 1: 1.

6. the method according to claim 3, wherein the reaction solvent in step (2) is an organic solvent, and the organic solvent is at least one of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, DMF, and DMSO.

7. The method according to claim 6, wherein the reaction temperature in the step (2) is 70 ℃ and the reaction time is 2 hours.

8. The process according to claim 3, wherein the molar ratio of the compound of formula II to sodium 1, 1-dicyanoethylene-2, 2-dithiolate in step (2) is 1: 2.3.

9. use of the multiple fused ring n-type semiconductor material of claim 1 in the preparation of an organic field effect transistor.

10. Use of the multiple fused ring n-type semiconductor material of claim 1 in the manufacture of a battery.

Technical Field

The invention relates to the field of materials, in particular to a preparation method and application of a multi-condensed ring n-type semiconductor material.

Background

The organic field effect transistor has the advantages of wide material source, more film forming technologies, low processing temperature, easy regulation and control of electrical properties, compatibility with a flexible substrate, suitability for batch production, low cost and the like. Among them, organic semiconductors have been most widely studied as active layers of organic field effect transistors.

The development of n-type semiconductor materials is still relatively delayed with respect to p-type semiconductor materials that have made some progress, mainly because the carriers of n-type semiconductor materials are electrons, which are very reactive with oxygen and water in air, meaning that electrons are trapped during transport and do not respond electrically. However, n-type semiconductor materials have very high research and application values as an indispensable part of bipolar complementary logic circuits. Organic semiconductor materials with ultra-low LUMO energy level can stabilize electronic carriers in air environment, and at present, the preparation method and related application of related materials are rarely mentioned in the prior art.

Therefore, a new n-type semiconductor material with an ultra-low LUMO level and matched with the work function of a metal electrode is needed and applied to the preparation of an organic field effect transistor or a battery.

Disclosure of Invention

In order to solve the problems, the invention provides a preparation method and application of a multi-condensed ring n-type semiconductor material, wherein the multi-condensed ring n-type semiconductor material has an ultralow LUMO energy level and can be matched with a metal electrode work function.

One of the purposes of the invention is to provide a multi-condensed ring n-type semiconductor material, and the technical scheme is as follows:

the poly-condensed-ring n-type semiconductor material has a molecular structural formula shown as a formula I:and the R is a solubilizing group.

Preferably, R is triisopropylsilyl or 2-octylthiophene or n-octylphenyl ether.

The second purpose of the invention is to provide a preparation method of the multi-condensed ring n-type semiconductor material, which comprises the following specific technical scheme:

the preparation method of the multi-condensed-ring n-type semiconductor material is characterized by comprising the following preparation steps of:

(1) reacting the formula III with a diketone compound to obtain a compound of a formula II;

(2) reacting the compound shown in the formula II with 1, 1-dicyanoethylene-2, 2-sodium dithiolate to obtain the compound shown in the formula I.

Preferably, the reaction solvent in step (1) is ethanol and acetic acid solution, the reaction temperature is 80 ℃, and the reaction time is 23 h.

Preferably, the volume ratio of ethanol to acetic acid is 1: 1.

preferably, the reaction solvent in step (2) is an organic solvent, and the organic solvent is at least one of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, DMF and DMSO.

Preferably, the reaction temperature of the step (2) is 70 ℃, and the reaction time is 2 h.

Preferably, the molar ratio of the formula II to the sodium 1, 1-dicyanoethylene-2, 2-dithiolate in the step (2) is 1: 2.3.

preferably, in the purification treatment of the compound II, the product obtained after the reaction is poured into ice water, then dichloromethane is used for extraction, an organic layer is collected and dried by anhydrous magnesium sulfate, and the purified product is obtained through filtration, rotary evaporation, column chromatography separation, rotary evaporation and vacuum filtration.

The invention also aims to provide the application of the multi-condensed ring n-type semiconductor material in the scheme in the preparation of the organic field effect transistor.

The fourth purpose of the invention is to provide the application of the multi-condensed-ring n-type semiconductor material in the scheme in the preparation of batteries, wherein the batteries comprise one or more of organic thin film solar batteries and perovskite batteries.

The invention has the advantages that: the material is formed by fusing a plurality of aromatic rings, has a larger plane structure, and four strong electron-withdrawing groups (cyano groups) can effectively reduce the LUMO energy level of molecules, thereby being an n-type semiconductor material with better development prospect.

Detailed Description

The present invention is further described in detail by the following examples, which should be understood that the present invention is not limited to the particular examples described herein, but is intended to cover modifications within the spirit and scope of the present invention.

Example 1

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 5 is as follows

Synthesis of Compound 4

Compound 1(174mg,0.47mmol) and 1, 6-bis (triisopropylsilyl) -1, 5-diyne-3, 4-dione (452mg,1.08mmol) were dissolved in 15ml of ethanol and 15ml of acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 5

Compound 4(988.6mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 2

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 7 is as follows

Synthesis of Compound 6

Compound 1(174mg,0.47mmol) and 1, 6-bis (tri-n-propylsilyl) -1, 5-diyne-3, 4-dione (452mg,1.08mmol) were dissolved in 15ml ethanol and 15ml acetic acid solution under argon and reacted at 80 ℃ for 23 h. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 7

Compound 6(989mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 3

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 9 is as follows

Synthesis of Compound 8

Compound 1(174mg,0.47mmol) and 1, 6-bis (triethylsilyl) -1, 5-diyne-3, 4-dione (345.6mg,1.08mmol) were dissolved in 15ml of ethanol and 15ml of acetic acid under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 9

Compound 8(806mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 4

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 11 is as follows

Synthesis of Compound 10

Compound 1(174mg,0.47mmol) and 1, 2-bis (5-n-octylthiophene) ethane-1, 2-dione (482mg,1.08mmol) were dissolved in 15ml of ethanol and 15ml of acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 11

Compound 10(1045mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 5

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 13 is as follows

Synthesis of Compound 12

Compound 1(174mg,0.47mmol) and 1, 2-bis (5-n-heptylthiophene) ethane-1, 2-dione (451.4mg,1.08mmol) were dissolved in 15ml ethanol and 15ml acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 13

Compound 12(988mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 6

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 15 is as follows

Synthesis of Compound 14

Under the protection of argon, compound 1(174mg,0.47mmol) and 1, 2-bis (5-n-hexyl)Thiophene) ethane-1, 2-dione (421.2mg,1.08mmol) was dissolved in 15ml ethanol and 15ml acetic acid solution and reacted at 80 ℃ for 23 h. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 15

Compound 14(932mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 7

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 17 is as follows

Synthesis of Compound 16

Compound 1(174mg,0.47mmol) and 1, 2-bis (5-tert-butylthiophene) ethane-1, 2-dione (360.7mg,1.08mmol) were dissolved in 15ml of ethanol and 15ml of acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 17

Argon shieldNext, compound 16(820mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 8

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 19 is as follows

Synthesis of Compound 18

Compound 1(174mg,0.47mmol) and 1, 2-bis (4-n-octylthiophene) ethane-1, 2-dione (482mg,1.08mmol) were dissolved in 15ml of ethanol and 15ml of acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 19

Compound 18(1045mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 9

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 21 is as follows

Synthesis of Compound 20

Compound 1(174mg,0.47mmol) and 1, 2-bis (4-n-heptylthiophene) ethane-1, 2-dione (451.4mg,1.08mmol) were dissolved in 15ml ethanol and 15ml acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring a product obtained after the reaction into ice water, extracting the product by using dichloromethane, collecting an organic layer, drying the organic layer by using anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, carrying out column chromatography separation, then carrying out rotary evaporation, and carrying out vacuum drying to obtain the product with the structure ofThe product of (1).

Synthesis of Compound 21

Compound 20(988mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

Example 10

This example discloses an electron acceptor having the following structure

The procedure for synthesizing the above electron acceptor compound 23 is as follows

Synthesis of Compound 22

Compound 1(174mg,0.47mmol) and 1, 2-bis (3- (octyloxy) phenyl) ethane-1, 2-dione (503mg,1.08mmol) were dissolved in 15ml ethanol and 15ml acetic acid solution under an argon atmosphere and reacted at 80 ℃ for 23 hours. After the reaction is finished, pouring the product obtained after the reaction into ice water, extracting the product by using dichloromethane, and collecting an organic layerThen drying with anhydrous magnesium sulfate, filtering, rotary steaming, separating by column chromatography, rotary steaming, and vacuum drying to obtain the final product with structure ofThe product of (1).

Synthesis of Compound 23

Compound 22(1085mg,1mmol) was reacted with sodium 1, 1-dicyanoethylene-2, 2-dithiolate (560mg,3mmol) in 30ml DMF under argon protection at 70 ℃ for 2 h. After the reaction is finished, performing rotary evaporation on DMF, performing column chromatography separation, performing rotary evaporation again, and performing vacuum drying to obtain the compound with the structure ofThe product of (1).

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.