KR101040779B1 - Benzimidazole-based copolymer and organic polymer thin film solar cells comprising the same - Google Patents

Abstract

The present invention provides a benzimidazole copolymer represented by Formula 1 below:

<Formula 1>

Wherein D is an electron donor, A is a benzimidazole derivative, and n is an integer from 10 to 150. The polymer compound according to the present invention can be spin-coated during application of the device, and can provide excellent light absorption, electrical conductivity, photovoltaic power, and luminescence properties such as organic polymer solar cells, organic thin film transistors, organic electroluminescent devices, and the like. It can be applied to various same areas.

Benzimidazole copolymer, absorption spectrum, organic thin film solar cell, organic thin film transistor

Description

Benzimidazole-based copolymer and organic polymer thin film solar cell device comprising same

The present invention relates to a novel benzimidazole copolymer and a device comprising the same, and more particularly, a benzimidazole copolymer having a narrow band gap as an organic semiconductor, an organic electroluminescence, or a solar absorbing material. It relates to an element.

In 1992, UCSB's Heeger first demonstrated the possibility of solar cells using organic polymers. It is a thin-film device made of a bulk heterojunction between organic polymer and C _{60. The} electron generated after the organic polymer receives the sunlight is the principle that C ₆₀ with high electron affinity attracts the electron and converts it into electricity. . Thus, the highest efficiency of organic polymer thin film solar cells using organic polymers currently reaches 6.5% ( Science , 2007, 307 , 222 ~ 225). However, the maximum efficiency of the solar cell using silicon is 39%, which is much higher than that of the organic polymer solar cell. Thus, the development of organic polymer solar cells with higher efficiency is required.

Accordingly, it is an object of the present invention to provide an organic polymer having a wider solar absorption band while being dissolved in an organic solvent and capable of spin coating at room temperature.

Another object of the present invention is to provide an organic polymer thin film solar cell device using the organic polymer as a solar absorbing material.

Another object of the present invention is to provide an organic thin film transistor using the organic polymer as an organic semiconductor material.

Another object of the present invention is to provide an organic electroluminescent device using the organic polymer as a light emitting material.

In order to achieve the above object, the present invention

It provides a benzimidazole-based copolymer represented by the formula (1):

<Formula 1>

Wherein D is an electron donor, A is a benzimidazole derivative, and n is an integer from 10 to 150.

In addition, in order to achieve the above other object, the present invention

Provided is an organic polymer thin film solar cell including the benzimidazole copolymer according to the present invention as a solar absorbing material.

In addition, in order to achieve the above other object, the present invention

Provided are an organic thin film transistor and an organic electroluminescent device comprising a benzimidazole copolymer according to the present invention as an organic semiconductor material and a light emitting material.

The polymer compound according to the present invention can be applied to an organic polymer solar cell, an organic thin film transistor, and an organic electroluminescent device because a spin coating process is possible when the device is applied, and excellent electrical conductivity, photovoltaic characteristics, and organic electroluminescence can be provided. have.

The present invention provides a benzimidazole copolymer represented by Formula 1 below:

Wherein D is an electron donor, A is a benzimidazole derivative, and n is an integer from 10 to 150.

The electron donor represented by D in Chemical Formula 1 may be represented by the following Chemical Formulas 2 to 5:

Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a linear or branched alkyl group of C _{1 -20} linear or branched alkoxy group of C _{1 -20} linear or branched alkoxyalkyl group in C _{1 -20,} and C _1-20 linear or branched alkoxyphenyl group.

Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a linear or branched alkyl group of C _{1 -20} linear or branched alkoxy group of C _{1 -20} linear or branched alkoxyalkyl group in C _{1 -20,} and C _1-20 linear or branched alkoxyphenyl group.

Wherein, R ₁ and R ₂ are each independently hydrogen atom, linear or branched alkyl group of C _{1 -20} linear or branched C _{1 -20} of the alkoxy group, linear or branched alkoxyalkyl group in C _{1 -20,} and C _1-20 linear or branched alkoxyphenyl group.

Wherein, R ₁ is a hydrogen atom, C _{1 -20} linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group in C _{1 -20} C for _{1 -20} of, and C _{1 -20} linear Or a branched alkoxyphenyl group.

On the other hand, the benzimidazole derivatives represented by A in Formula 1 may be represented by Formulas 6 to 9 more specifically:

Wherein, R ₁ and R ₂ are each independently a hydrogen atom, a ketone group, a linear or branched alkyl group of C _{1 -20} linear or branched alkoxy group of C _{1 -20} linear or branched C _{1 -20} of the type alkoxy alkyl group, and one selected from a linear or branched alkoxy group of C _{1 -20.}

Wherein, R _1, R _2, R _3, R _4, and R ₅ are each independently hydrogen, hydroxyl, C _{1 -20} linear or branched alkyl group, a linear or branched alkoxy group, C of C _1-20 of one _{1 -20} linear or branched alkoxyalkyl group, and selected from among linear or branched alkoxy group of C _{1 -20} of.

Wherein, R ₁ and R ₂ are each independently a hydrogen atom, a ketone group, a linear or branched alkyl group of C _{1 -20} linear or branched alkoxy group of C _{1 -20} linear or branched C _{1 -20} of the type alkoxy alkyl group, and one selected from a linear or branched alkoxy group of C _{1 -20.}

Wherein, R _1, R _2, R _3, R _4, and R ₅ are each independently hydrogen, hydroxyl, C _{1 -20} linear or branched alkyl group, C _{1 -20} linear or branched alkoxy group, C of the one _{1 -20} linear or branched alkoxyalkyl group, and selected from among linear or branched alkoxy group of C _{1 -20} of.

More specifically, examples of the compound having the electron donor and the benzimidazole derivative at the same time include benzimidazole copolymers represented by the following formulas (10) to (22) and (24 to 29). In the formula, n is an integer from 10 to 150.

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On the other hand, as a compound having the electron donor and the benzimidazole derivative at the same time, a benzimidazole-based copolymer represented by the following formula (23) or (30) can be exemplified:

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or

Wherein m and n are integers from 1 to 150.

The organic polymer is fluorene, cyclopentadithiophene, thiophene, carbazole, 4 H -cyclopenta [ def ] phenanthrene as an electron donor benzimidazole-2-spirocyclohexane, 2,2-dihexyl -2 H-benzimidazole, di (between en-2-yl) benz imidazole-2-hexyl spy cyclohexane, 2,2-dimethyl-4,7-di (2-carbonyl between) -2 H -benzimidazole is included as a benzimidazole derivative which is an electron acceptor.

The benzimidazole copolymer according to the present invention preferably has a number average molecular weight of 6,000-31,000 and a mass average molecular weight of 10,000-158,000.

The polymer of the present invention has a characteristic of absorbing a longer wavelength side than the conventional polymer for solar cells. That is, the characteristics of absorbing light in the wavelength band that conventional solar cells do not absorb appears.

The benzimidazole-based copolymer of the present invention is well dissolved in a general organic solvent and spin-coating is possible at room temperature. Thus, an organic polymer thin film solar cell or the like may be manufactured on a plastic substrate that can be bent through a simple process. Can be.

Benzimidazole-based copolymer represented by the general formula (1) of the present invention can be synthesized using conventional methods known in the art, it is not particularly limited. More specifically, the compounds represented by Formulas 10 to 30 may be synthesized according to the following Schemes 1 to 21.

As shown in Scheme 1, 2,7-dibromofluorene (Formula 1a) and hexylbromide are reacted with sodium hydroxide to obtain 9,9-dihexyl-2,7-dibromofluorene (Formula 1b) And reacting 9,9-dihexyl-2,7-dibromofluorene (Formula 1b) with bis (pinacolato) diboron to obtain 9,9-dihexyl-2,7-bis (4,4 , 5,5-tetramethyl-1,3,2 Sabo Lorraine dioxane-2-yl) -9 H - fluorene (formula 1c) was obtained. 2,1,3-benzocyadiazole (Formula 1d) was reacted with bromine to give 4,7-dibromo-2,1,3-benzocyadiazole (Formula 1e), wherein 4, 7-Dibromo-2,1,3-benzocyadiazole (Formula 1e) was reacted with sodium borohydride to give 3,6-dibromo-1,2-benzenediamine (Formula 1f) And reacting 3,6-dibromo-1,2-benzenediamine (Formula 1f) with cyclohexanone to 4,7-dibromobenzimidazole-2 ( 3H ) -spirocyclohexane 1 g) was obtained and the 4,7-dibromobenzimidazole-2 ( 3H ) -spirocyclohexane (1 g) was reacted with manganese dioxide to give 4,7-dibromobenzimidazole-2-spiro. Obtain cyclohexane (Formula 1h), and the 4,7-dibromobenzimidazole-2-spirocyclohexane (Formula 1h) and 9,9-dihexyl-2,7-bis (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolane-2-yl) -9 H -Fluorene (Formula 1c) a Suzuki coupling reaction through the ring poly [2,7- (9,9-dimethyl-hexyl H -9-fluorenyl) - alt -4,7- (a benzimidazol-2-Spy Cyclohexane)] (Formula 1i).

As shown in Scheme 2, 3-bromosiophene (Formula 2a) is reacted with ethyl formate to obtain di (3-cyenyl) methanol (Formula 2b), and the di (3-cyenyl) Methanol (Formula 2b) was reacted with lithium aluminum hydride and aluminum (III) chloride to obtain 3- (3-cyenylmethyl) thiophene (Formula 2c), and 3- (3-cyenylmethyl) Reacting thiophene (Formula 2c) with N -bromosuccinimide to give 2-bromo-3-[(2-bromo-3-cyenyl) methyl] thiophene (Formula 2d) 2-bromo-3-[(2-bromo-3-cyenyl) methyl] thiophene (Formula 2d) was reacted with n -butyllithium and copper (II) chloride to give 4 H -cyclopenta [2, 1-b: 3,4-b '] diocyphene (Formula 2e) was obtained, and the 4H -cyclopenta [2,1-b: 3,4-b'] dithiophene (Formula 2e) 2-ethyl-hexyl bromide is reacted with sodium hydroxide to 4,4-bis (2-ethylhexyl) -4 H - company Claw-penta [2,1-b: 3,4-b '] thiophene to give the dies between (Formula 2f), and wherein the 4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1 b: 3,4-b '] dithiophene (Formula 2f) is reacted with isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane to give 4,4-bis ( 2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lorraine-2-yl) -4 H - cyclopenta -[2,1-b: 3,4-b '] dithiophene (Formula 2g) was obtained, and the 4,4-bis (2-ethylhexyl) -2,6-bis (4', 4 '). between: '[3,4-b 2,1- b], 2'- dioxane Sabo Lorraine-2-yl) -4 H - - cyclopenta die, 5', 5'-tetramethyl-1 ', 3 Open (Formula 2g) and 4,7-Dibromobenzimidazole-2-spirocyclohexane (Formula 1h) were subjected to poly [2,6- (4,4-bis (2-ethylhexyl) through Suzuki coupling ) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7- (benz cyclohexane-imidazole-2-Spy)] (formula 2h) the Obtained All.

As shown in Scheme 3, 1,4-cyclohexanediol (Formula 3a) is reacted with 1.6M Jones reagent to obtain 4-hydroxycyclohexanone (Formula 3b), and 4-hydroxycyclohexane On (Formula 3b) is reacted with 3,6-dibromo-1,2-benzenediamine (Formula 1f) to 4,7-dibromobenzimidazole-2 ( 3H ) -spirocyclohexane-4 ' -Ol (Formula 3c) was obtained and the 4,7-dibromobenzimidazole-2 ( 3H ) -spirocyclohexane-4'-ol (Formula 3c) was reacted with manganese dioxide to give 4,7-dive Obtain lomobenzimidazole-2-spirocyclohexane-4'-ol (Formula 3d), and the 4,7-dibromobenzimidazole-2-spirocyclohexane-4'-ol (formula 3d) and 9,9-dimethyl-hexyl-2,7-bis (4,4,5,5-tetramethyl-1,3,2 Sabo Lorraine dioxane-2-yl) -9 H - fluorene (formula 1c) via a Suzuki coupling reaction, poly [2,7- (9,9-dimethyl-hexyl -9 H -Fluorene) -alt- 4,7- (benzimidazole-2-spirocyclohexane-4'-ol)] (Formula 3e).

As shown in Scheme 4, 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'- dioxane Sabo Lorraine-2-yl) -4 H - cyclopenta - [2,1-b: 3,4- b '] thiophene between the die (formula 2g) and 4,7-dibromo-benzimidazol-2-Spy the rosayi chloride-hexane-4'-ol (formula 3d) via a Suzuki coupling reaction, poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] dithiophene) -alt- 4,7- (benzimidazole-2-spirocyclohexane-4'-ol)] (Formula 4a).

As shown in Scheme 5, 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'- dioxane Sabo Lorraine-2-yl) -4 H - cyclopenta - [2,1-b: 3,4- b '] thiophene between the die (formula 2g) and 4,7-dibromo-benzimidazol-2-Spy Cyclocyclohexane (Formula 1h) and 4,7-Dibromobenzimidazole-2-spirocyclohexane-4'-ol (Formula 3d) were subjected to poly [2,6- (4,4) through Suzuki coupling. - bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between die) -co-4,7- (benz imidazol-2-cyclopenten to spy hexane ) -co-4,7- (benzimidazole-2-spirocyclohexane-4'-ol)] is obtained.

As shown in Scheme 6, 4,7-dibromobenzimidazole-2-spirocyclohexane-4'-ol (Formula 3d) is reacted with chloromethylmethyl ether (Formula 6a) to give 4,7-dive Lomo-4 '-(methoxymethoxy) benzimidazole-2-spirocyclohexane (Formula 6b) was obtained, and the 4,7-dibromo-4'-(methoxymethoxy) benzimidazole- 2-spirocyclohexane (Formula 6b) and 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxane Sabo Lorraine-2-yl) -4 H - cyclopenta - [2,1-b: 3,4- b '] thiophene between the die (formula 2g) poly through a Suzuki coupling reaction, [2, 6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7- (benzimidazole- 2-Spyro- (4 '-(methoxymethoxy) -cyclohexane)] is obtained.

As shown in Scheme 7, 1,4-cyclohexanedione mono-ethylene ketal (Formula 7a) was reacted with sodium borohydride to produce 1,4-dioxaspiro [4.5] decan-8-ol ( Formula 7b) was obtained, and the 1,4-dioxaspiro [4.5] decan-8-ol (Formula 7b) and 2-ethylhexylbromide were reacted with sodium hydride to give 8-[(2-ethylhexyl) Oxy] -1,4-dioxaspiro [4.5] decane (Formula 7c) was obtained, and the 8-[(2-ethylhexyl) oxy] -1,4-dioxaspiro [4.5] decane (formula) 7c) is reacted with acetic acid to obtain 4-[(2-ethylhexyl) oxy] cyclohexanone (Formula 7d), and 4-[(2-ethylhexyl) oxy] cyclohexanone (Formula 7d) is added to 3 4,7-Dibromo-4 '-[(2-ethylhexyl) oxy] benzimidazole-2 ( 3H ) -spy by reacting with 6-dibromo-1,2-benzenediamine (Formula 1f) Obtain cyclocyclohexane (Formula 7e), the 4,7-dibromo-4 '-[(2- Ethylhexyl) oxy] benzimidazole sol-2 ( 3H ) -spirocyclohexane (Formula 7e) was reacted with manganese dioxide to give 4,7-dibromo-4 '-[(2-ethylhexyl) oxy] benzimi Obtained dazole-2-spirocyclohexane (Formula 7f), and the 4,7-dibromo-4 '-[(2-ethylhexyl) oxy] benzimidazole-2-spirocyclohexane (Formula 7f) And 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxaborolane-2-yl ) - 4 H - cyclopenta - [2,1-b: 3,4- b '] thiophene between the die (formula 2g) via the Suzuki coupling reaction, poly [2,6- (4,4-bis (2 -ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between die) - alt-4,7- (benz-imidazole-2-spyware - (4' - ( (2 ''-ethylhexyl) oxy))-cyclohexane)] is obtained.

As shown in Scheme 8, 3-bromosiophene (formula 8a) and 1-hexanol are reacted with sodium hydride to obtain 3- (hexyloxy) thiophene (formula 8b), wherein 3- ( Hexyloxy) thiophene (Formula 8b) is reacted with N -bromosuccinimide to yield 2-bromo-3- (hexyloxy) thiophene (Formula 8c), and 2-bromo-3 -(Hexyloxy) thiophene (formula 8c) was obtained through Grignard reaction to obtain 3,3'-dihexyloxy- [2,2'-bithiophene] (formula 8d), wherein 3, 3'-dihexyloxy- [2,2'-bithiophene] (Formula 8d) is reacted with isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxabolorine 5,5'-di (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) -3,3'-dihexyloxy- [2,2'-bi Thiophene] (Formula 8e), wherein the 5,5'-di (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) -3,3'- Dihexyloxy- [2,2'-bithiophene] ( (8e) and 4,7-Dibromobenzimidazole-2-spirocyclohexane (Formula 1h) through the Suzuki coupling reaction poly [5,5 '-(3,3'-dihexyloxy- ( 2,2'-Biothiophene))- alt- 4,7- (benzimidazole-2-spirocyclohexane)] (Formula 8f).

As shown in Scheme 9, ethyl formate (Formula 9a) is reacted with octyl magnesium bromide to obtain heptadecan-9-ol (Formula 9b), and the heptadecan-9-ol (Formula 9b) is represented by p − Reaction with toluenesulfonyl chloride yields 1-octynonyl 4-methylbenzenesulfonate (Formula 9c). Ciophene (Formula 9d) is reacted with isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane to 4,4,5,5-tetramethyl-2- (2 ' -Cyenyl) -1,3,2-dioxaborolane (Formula 9e), wherein 4,4,5,5-tetramethyl-2- (2'-cyenyl) -1,3, 2-dioxaborolane (formula 9e) and 4,7-dibromobenzimidazole- 2-spirocyclohexane (formula 1h) through a Suzuki coupling reaction to 4,7-di (cyen-2'-yl) ) -Benzimidazole-2-spirocyclohexane (Formula 9f) was obtained, and the 4,7-di (cyen-2'-yl) -benzimidazole-2-spirocyclohexane (Formula 9f) was obtained. Is reacted with N -bromosuccinimide to give 4,7-di (2'-bromosien-5'-yl) -benzimidazole-2-spirocyclohexane (9 g). Reacting 4,4'-dibrobiphenyl (Formula 9h) with nitric acid to give 4,4'-dibromo-2-nitro-1,1'-biphenyl (Formula 9i), wherein 4,4 Reacting '-dibromo-2-nitro-1,1'-biphenyl (Formula 9i) with triethyl phosphite to give 2,7-dibromo-9 H -carbazole (Formula 9j), 2,7-Dibromo-9 H -carbazole (Formula 9j) is reacted with 1-octylnonyl 4-methylbenzenesulfonate (Formula 9c) to give 2,7-dibromo-9- (1'-octylnonyl) -9 H - carbazole (formula 9k) to obtain, and the 2,7-dibromo-9- (1'-octyl-nonyl) -9 H - carbazol-isopropoxy-4,4 (formula 9k), Reacted with 5,5-tetramethyl [1,3,2] dioxaborolane and 9- (1-octylnonyl) -2,7-bis (4 ', 4', 5 ', 5'-tetramethyl-1 ', 3', 2'-dioxane to Sabo LAN-2'-yl) -9 H - carbazol obtain a sol (formula 9l), and the 9- (1-octyl-nonyl) 2,7-bis (4 ' , 4 ', 5', 5'-tetramethyl-1 ', 3', 2'-dioxane to Sabo LAN-2'-yl) -9 H - carbazole ( 9l) and 4,7-di (2'-bromosien-5'-yl) -benzimidazol-2-spirocyclohexane (9 g) were subjected to poly [2,7- a benzimidazole-2'spy - (9- (1'-octyl-nonyl) -9 H-carbazole) - alt -5,5- (4 ', 7'- die (yen between 2-yl) Cyclohexane)] (formula 9m).

As shown in Scheme 10, 4,4,5,5-tetramethyl-2- (2'-cyenyl) -1,3,2-dioxaborolane (Formula 9e) and 4,7-dibromo -4 '-[(2-ethylhexyl) oxy] benzimidazole-2-spirocyclohexane (Formula 7f) via 4,7-di (cyen-2'-yl) -benz via Suzuki coupling reaction Obtain imidazole-2-spiro-4 ''-[(2 '''-ethylhexyl) oxy] -cyclohexane (Formula 10a), wherein 4,7-di (cyen-2'-yl) -Benzimidazole-2-spiro-4 ''-[(2 '''-ethylhexyl) oxy] -cyclohexane (Formula 10a) was reacted with N -bromosuccinimide to give 4,7-di ( 2'-Bromocyen-5'-yl) -benzimidazole-2-spiro-4 ''-[(2 '''-ethylhexyl) oxy] -cyclohexane (Formula 10b) was obtained, and 4,7-di (2'-bromosien-5'-yl) -benzimidazole-2-spiro-4 ''-[(2 '''-ethylhexyl) oxy] -cyclohexane (Formula 10b ) And 9- (1-octylnonyl) -2,7-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2' - in dioxane Sabo LAN-2'-yl) -9 H-carbazole (formula 9l) a Suzuki coupling reaction through the poly [2,7- (9- (1'-octyl-nonyl) -9 H-carbazole ) - alt -5,5- (4 ', 7'- die (between en-2-yl) benz-imidazole-2'-spy-4''-((2''' - ethylhexyl) oxy ) -Cyclohexane)] is obtained.

Cyclopenta [def] phenanthrene (Formula 11a) of 8,9- dihydro -4 H via the hydrogenation - -, 4 H, as shown in the above scheme to give the cyclopenta [def] phenanthrene (formula 11b), and , 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] by bromination of the 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 11b) A phenanthrene (formula 11c) was obtained and 2,6-dive was reacted with 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (formula 11c) with bromine. Homes-hydroxide, the cyclopenta [def] phenanthrene (formula 11d) and 2-ethylhexyl bromide-4 H-cyclopenta [def] phenanthrene (formula 11d) to obtain, and the 2,6-dibromo -4 H It is reacted with sodium 2,6-dibromo-4,4-bis (2-ethylhexyl) -4 H - to give the cyclopenta [def] phenanthrene (formula 11e), and then, the 2,6 Bromo-4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene (formula 11e) of bis (pinacolato) boron was reacted with dimethyl 4,4-bis (2- ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lauren-2'-yl) -4 H - cyclopenta [ def ] phenanthrene (formula 11f), wherein the 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lauren-2'-yl) -4 H - cyclopenta [de f] phenanthrene (formula 11f) and 4,7-di (2'-bromo-5'-yl simulated two yen) benzamide cyclohexane-imidazole-2-Spy through poly (formula 9g) a Suzuki coupling reaction, [(2,6- (4,4-bis (2'-ethylhexyl) -4 H - cyclopenta [def] Phenanthrene))- alt- (5,5- (4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane))) (Formula 11 g) is obtained. .

As shown in Reaction Scheme 12, 2,6-dibromo -4 H-cyclopenta [def] phenanthrene-2,6-dibromo -4 H through the (formula 11d) the oxidation-cyclopenta [def] phenanthrene Tren-4-one (Formula 12a) was obtained, and the 2,6-dibromo- 4H -cyclopenta [ def ] phenanthren-4-one (Formula 12a) was converted to phenol, zinc chloride (II), and hydrogen chloride gas. and reacting 2,6-dibromo-4,4-bis (4'-hydroxyphenyl) -4 H - to give the cyclopenta [def] phenanthrene (formula 12b), and wherein the 2,6-dibromo- 4,4-bis (4'-hydroxyphenyl) -4 H - cyclopenta [def] phenanthrene-2,6-dibromo-4,4-bis (formula 12b) was reacted with 2-ethylhexyl bromide ( 4 '- ((2''- ethylhexyl) oxy) phenyl) -4 H - to give the cyclopenta [def] phenanthrene (Chemistry learning 12c), and wherein the 2,6-dibromo-4,4-bis ( 4-bis-cyclopenta [def] phenanthrene (formula 12c), (- ((2- ethylhexyl) oxy) phenyl) -4 H Reacts with nacollato) diboron 4,4-bis (4-((2-ethylhexyl) oxy) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl- 1 ', 3', 2'-dioctyl Sabo Lauren-2'-yl) -4 H-cyclopenta [def] phenanthrene give the Transistor (formula 12d), and wherein the 4,4-bis (4 - ((2 Ethylhexyl) oxy) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxabororen-2'-yl) -4 H -Suzuki coupling cyclopenta [ def ] phenanthrene (Formula 12d) with 4,7-di (2'-bromosien-5'-yl) -benzimidazole-2-spirocyclohexane (Formula 9g) through the reaction poly [(2,6- (4,4-bis (4 '- ((2''- ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene)) - alt - ( 5,5- (4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane))] is obtained.

As shown in Scheme 13, thiophene (Formula 9d) is reacted with trimethyltin chloride to give 2,5-bis (trimethylstenyl) thiophene (Formula 13a), and 2-bromo-3- 4,7-bis- (3-hexyloxy-thiophene by reacting (hexyloxy) thiophene (Formula 8c) with 4,7-dibromobenzimidazole-2-spirocyclohexane (Formula 1h) 2-yl) -benzimidazole-2-spirocyclohexane (Formula 13b) to give 4,7-bis- (3-hexyloxy-thiophen-2-yl) -benzimidazole- 2-Spyrocyclohexane (Formula 13b) was reacted with N -bromosuccinimide to give 4,7-bis- (5-bromo-3-hexyloxy-thiophen-2-yl) benzimidazole- 2-Spyrocyclohexane (Formula 13c) was obtained, and the 4,7-bis- (5-bromo-3-hexyloxy-thiophen-2-yl) benzimidazole-2-spirocyclohexane Formula (13c) and 2,5-bis (trimethylstenyl) thiophene ( Formula 13a) was subjected to poly [5,5 ''-(4- (hexyloxy) -4 ''-(hexyloxy) -2,2 ', 5', 2 ''-via a stlelet coupling reaction. Tersiophen) -alt- 4,7- (benzimidazole-2-spirocyclohexane)] (Formula 13d).

As shown in Scheme 14, 3- (hexyloxy) thiophene (Formula 8b) is reacted with N -bromosuccinimide to give 2,5-dibromo-3- (hexyloxy) thiophene 14a), 3,6-dibromo-1,2-benzenediamine (Formula 1f) and dihexyl ketone (Formula 14b) were reacted to 4,7-dibromo-2,2-dihexyl-2 , 3-dihydro-1 H -benzimidazole (Formula 14c) was obtained, and the 4,7-dibromo-2,2-dihexyl-2,3-dihydro-1 H -benzimidazole (Formula 14c) was obtained. 14c) is reacted with manganese dioxide to give 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d), wherein the 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) and 2,5-bis (trimethylstenyl) thiophene (Formula 13a) and 2,5-dibromo-3- (hexyloxy) thiophene (Formula 14a) Poly [(2'-5- (3'-hexyloxy) -5 '-(2-cyenyl) Io pen) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, TOHT-co- BCHT10 ( formula 14e ), TOHT-co-BCHT30 (Formula 14f), TOHT-co-BCHT50 (Formula 14g), TOHT-co-BCHT70 (Formula 14h), TOHT-co-BCHT90 (Formula 14i) are obtained.

As shown in Scheme 15, 4H -cyclopenta [2,1-b: 3,4-b '] diocyopene (Formula 2e) is reacted with iodomethane to give 4,4-dimethyl- 4H. -Cyclopenta [2,1-b: 3,4-b '] diocyopene (Formula 15a) to obtain the above 4,4-dimethyl- 4H -cyclopenta [2,1-b: 3, 4-b '] dithiophene (formula 15a) is reacted with isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane to give 4,4-dimethyl-2,6 - bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lorraine-2-yl) -4 H - cyclopenta - [2,1-b: 3 , 4-b '] dithiophene (Formula 15b) to obtain 4,4-dimethyl-2,6-bis (4', 4 ', 5', 5'-tetramethyl-1 ', 3 ', 2'-dioctyl Sabo Lorraine-2-yl) -4 H - cyclopenta - [2,1-b: 3,4- b '] thiophene between the die (formula 15b) and 4,7-dibromo-benzimidazole The polyazole [2,6- (4,4-di] was reacted with the dazol-2-spirocyclohexane (Formula 1h) through Suzuki coupling. Butyl -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7- (benz cyclohexane)] (formula 15c to the imidazole-2 Spy) To obtain.

As shown in Scheme 16, 4,4-dimethyl-2,6-bis (4 ′, 4 ′, 5 ′, 5′-tetramethyl-1 ′, 3 ′, 2′-dioxaborolane-2 -yl) -4 H - cyclopenta - [2,1-b: 3,4- b '] thiophene between the die (formula 15b) and 4,7-dibromo-2,2-dimethyl-hexyl -2 H - benzamide The imidazole (Formula 14d) was subjected to poly [2,6- (4,4-dimethyl- 4H -cyclopenta [2,1-b: 3,4-b '] diothiophene via Suzuki coupling reaction. alt- 4,7- (2,2-dihexyl- 2H -benzimidazole)] (Formula 16a).

As shown in Scheme 17, 2,5-bis (trimethylstenyl) thiophene (Formula 13a) and 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) The poly [2,5- (thiophene) -alt- 4,7- (2,2-dihexyl- 2H -benzimidazole)] (Formula 17a) was obtained through a Suzuki coupling reaction.

As shown in Scheme 18, 2,2'-bithiophene (Formula 18a) is reacted with trimethyltin chloride to give 5,5'-bis (trimethylstenyl) -2,2'-biothiophene ( Formula 18b), wherein 5,5'-bis (trimethylstenyl) -2,2'-bithiophene (Formula 18b) and 4,7-dibromo-2,2-dihexyl- 2H - benzimidazole (formula 14d) via a Suzuki coupling reaction is poly [5,5 '- (thiophene between 2,2 Bar) - alt -4,7- (2,2- dimethyl-hexyl -2 H - Benzimidazole)] (Formula 18c).

As shown in Scheme 19, thiophene (Formula 9d) is reacted with tributyltin chloride to give 2- (tributylstenyl) thiophene (Formula 19a), and between 2- (tributylstenyl) Offen (Formula 19a) and 4,7-Dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) were subjected to 2,2-dihexyl-4,7-di ( to give the benzimidazole (formula 19b), and the 2,2-hexyl 4,7-di (carbonyl) -2 H between 2-carbonyl) -2 H between 2-benzimidazole (general formula 19b) is reacted with N -bromosuccinimide to give 4,7-bis (5-bromo-2-cyenyl) -2,2-dihexyl-2 H -benzimidazole (Formula 19c) And 4,7-bis (5-bromo-2-cyenyl) -2,2-dihexyl- 2H -benzimidazole (Formula 19c) and 2,5-bis (trimethylstenyl) Ciophene (Formula 13a) was subjected to poly [5,5 ''-(2,2 ', 5', 2 ''-terthiophene)- alt- 4,7- (2,2-dihexyl-2 H -benzimidazole)] is obtained.

As shown in Scheme 20, 2,7-dibromo-9 H -carbazole (9j) and 2-ethylhexylbromide are reacted with sodium hydride to give 2,7-dibromo-9- (2-ethyl hexyl) -9 H - to give the carbazole (formula 20a), and wherein the 2,7-dibromo-9- (2-ethylhexyl) -9 H - carbazole (formula 20a) a-isopropoxy-4,4 9- (2-ethylhexyl) -2,7-bis (4 ', 4', 5 ', 5'-tetramethyl- was reacted with, 5,5-tetramethyl [1,3,2] dioxaborolane. 1 ', 3', 2'dioxaborolan-2'-yl) -9 H -carbazole (Formula 20b) was obtained, and the 9- (2-ethylhexyl) -2,7-bis (4 ' , 4 ', 5', 5'-tetramethyl-1 ', 3', 2'-dioctyl Sabo to LAN-2'-yl) -9 H - carbazole (formula 20b) and 4,7-bis (5 -Bromo-2-cyenyl) -2,2-dihexyl- 2H -benzimidazole (Formula 19c) was subjected to poly [2,7- (9- (2-ethylhexyl)) via Suzuki coupling reaction. -9 H - carbazole) - alt -5,5- (4 ', 7'- die (between en-2-yl) -2,2-hexyl -2 H - benzimidazole)] (formula 20c) To To obtain.

As shown in Scheme 21, 4H -cyclopenta [2,1-b: 3,4-b ′] dithiophene (Formula 2e) is reacted with hexyl bromide to give 4,4-dihexyl- 4H − Cyclopenta [2,1-b: 3,4-b '] diocyopene (Formula 21a) was obtained, and the 4,4-dihexyl- 4H -cyclopenta [2,1-b: 3,4 -b '] dithiophene (Formula 21a) is reacted with N -bromosuccinimide to give 2,6-dibromo-4,4-dihexyl- 4H -cyclopenta [2,1-b: 3, 4-b '] dithiophene (formula 21b) is obtained, wherein the 2,6-dibromo-4,4-dihexyl- 4H -cyclopenta [2,1-b: 3,4-b'] Dithiophene (Formula 21b) and 4,7-Dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) and 2,5-bis (trimethylstenyl) thiophene (Formula 13a) the steel rail coupling through the coupling reaction; poly [(5 ', 6- (4,4-dimethyl-hexyl) -2- (2 ' between carbonyl) -4 H - cyclopenta [2,1-b: 3, 4-b '] dithiophene) -co- (5', 7- (2,2-dihexyl) -4- (2'-cyenyl) -2 H -benzimidazole)] s, PCPDTT-co-BCHT10 (Formula 21c), PCPDTT-co-BCHT30 (Formula 21d), PCPDTT-co-BCHT50 (Formula 21e), PCPDTT-co-BCHT70 (Formula 21f), PCPDTT -co-BCHT90 (21 g) is obtained.

The present invention also relates to a device using the organic polymer as an organic semiconductor, organic electroluminescence, or solar light absorbing material.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are intended to illustrate the present invention in detail, and the scope of the present invention is not limited by the following examples.

Example

Example  One

Poly [2,7- (9,9- Dihexyl -9 H - Fluorene ) - alt -4,7- ( Benzimidazole -2- Spirosai Clohexane)]

1) Synthesis of 9,9-dihexyl-2,7-dibromofluorene (Formula 1b)

5 g (15.43 mmol) of 2,7-dibromofluorene (Formula 1a) and 70 mg (0.31 mmol) of triethylbenzylammonium chloride were dissolved in 40 ml of dimethyl sulfoxide, and then 4.77 ml (33.95 mmol) of 1-bromohexane was added. After stirring at room temperature for 5 minutes, 1.36 ml (33.95 mmol) of 50% sodium hydroxide was added thereto, and the mixture was stirred at 80 ° C. for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite, and distilling off the solvent under vacuum distilled off the product, the product was separated by column chromatography. 5.82 g (76%) of a colorless solid were obtained.

R _f = 0.8 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.53 (d, 6H), 7.46 (d, 6H), 7.43 (s, 2H), 1.98-1.78 (m, 4H), 1.20-0.92 (m, 12H), 0.80 (t, 6H), 0.66-0.46 (m, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 153.4, 139.9, 131.0, 127.1, 122.3, 121.9, 56.6, 41.1, 32.3, 30.5, 24.5, 23.4, 14.8

2) 9,9-dimethyl-hexyl-2,7-bis (4,4,5,5-tetramethyl-1,3,2 Sabo Lorraine dioxane-2-yl) -9 H - fluorene (formula 1c) Synthesis of

0.5 g (1.02 mmol) of the compound of Formula 1b, 4.86 g (19.15 mmol) of bis (pinacolato) diborone and 0.90 g (3.55 mmol) of potassium acetate were dissolved in 8 ml of N , N -dimethylformamide. 50 mg (0.06 mmol) of 1,1′-bis (diphenylphosphino) ferrocenepalladium (II) dichloro dichloromethane complex was added at room temperature, followed by stirring at 60 ° C. for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite, and distilling off the solvent under vacuum distilled off the product, the product was separated by column chromatography. 0.48 g (80%) of white crystals were obtained.

R _f = 0.6 (SiO ₂ , Ethyl acetate: hexane = 1:15)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.81 (d, 2H), 7.74 (s, 2H), 7.73 (d, 2H), 2.16-1.92 (m, 4H), 1.38 (s, 24H), 0.76 ( t, 6H), 0.62-0.46 (m, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 150.1, 143.6, 133.3, 128.6, 119.0, 83.4, 54.9, 39.8, 31.1, 29.3, 24.6, 23.2, 22.2, 13.7

3) Synthesis of 4,7-Dibromo-2,1,3-benzocyadiazole (Formula 1e)

10g (73.43mmol) of 2,1,3-benzocyadiazole (Formula 1d) was dissolved in 150ml (1.32mol) of 48% bromic acid, and then 7.49ml (220.29mmol) of 99.70ml of 48% bromine at room temperature. Was added slowly with. It stirred at 100 degreeC for 6 hours. After cooling to room temperature and neutralized by the addition of saturated sodium bisulfite, the resulting precipitate was filtered off, washed with distilled water and washed with cold ether. 20.05 g (92%) of a milky solid were obtained.

R _f = 0.7 (SiO ₂ , ethyl acetate: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.73 (s, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 153.2, 132.6, 114.2

HRMS, m / e, C ₆ H ₂ Br ₂ N ₂ S, 291.8309 (calcd. 291.8305)

4) Synthesis of 3,6-Dibromo-1,2-benzenediamine (Formula 1f)

3.5 g (11.91 mmol) of the compound of Chemical Formula 1e thus obtained were dissolved in 400 ml of ethanol, and then 8.11 g (214.31 mmol) of sodium borohydride was added little by little at 0 ° C. After stirring for 10 minutes at 0 ℃ stirred at room temperature for 3 hours. After cooling to 0 ° C., 100 ml of distilled water was added, followed by vacuum distillation. The remaining residue was extracted with ether and distilled water and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 3.05 g (96%) of a milky solid was obtained.

R _f = 0.3 (SiO ₂ , ethyl acetate: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 6.84 (s, 2H), 3.89 (br, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 134.0, 123.5, 109.9

HRMS, m / e, C ₆ H ₆ Br ₂ N ₂ , 263.8901 (calcd. 263.8898)

5) Synthesis of 4,7-Dibromobenzimidazole-2 ( 3H ) -spirocyclohexane (Formula 1g)

3.02 g (11.36 mmol) of the compound of Formula 1f and 1.18 ml (11.36 mmol) of cyclohexanone thus obtained were dissolved in 75 ml of toluene, followed by stirring at 100 ° C. for 6 hours. The solvent was distilled off in vacuo and the remaining liquid residue was separated by column chromatography. 3.11 g (79%) of a yellow liquid were obtained.

R _f = 0.4 (SiO ₂ , Ethyl acetate: hexane = 1:15)

¹ H NMR (300 MHz, Acetone-D ₆ ) δ 6.49 (s, 2H), 5.42 (br, 2H), 1.86-1.74 (m, 4H), 1.73-1.60 (m, 4H), 1.48-1.36 (m , 2H)

¹³ C NMR (75 MHz, Acetone-D ₆ ) δ 153.2, 132.6, 114.2

HRMS, m / e, C ₆ H ₆ Br ₂ N ₂ , 263.8901 (calcd. 263.8898)

6) Synthesis of 4,7-dibromobenzimidazole-2-spirocyclohexane (Formula 1h)

0.77 g (2.23 mmol) of the compound of Formula 1 thus obtained was dissolved in 20 ml of methylene chloride, and then 2.73 g (26.7 mmol) of 85% manganese dioxide (IV) was added at room temperature. After stirring for 1 hour at room temperature, the mixture was extracted with methylene chloride and distilled water and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 0.61 g (80%) of a yellow solid was obtained.

R _f = 0.3 (SiO ₂ , ethyl acetate: hexane = 1:15)

¹ H NMR (300 MHz, Acetone-D ₆ ) δ 7.43 (s, 2H), 2.00-1.84 (m, 4H), 1.82-1.70 (m, 2H), 1.70-1.58 (m, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.1, 136.0, 119.0, 107.5, 32.8, 25.7, 24.7

HRMS, m / e, C ₁₂ H ₁₂ Br ₂ N ₂ , 341.9365 (calcd. 341.9367)

Synthesis of [alt -4,7- (benz cyclohexane-imidazole-2-Spy) 2,7 (9,9-dimethyl-hexyl -9 H - - fluorene)] (formula 1i) 7) Poly

Thus obtained 176 mg (0.51 mmol) of the compound of Formula 1h, 300 mg (0.51 mmol) of the compound of Formula 1c, 2.4 ml of 2M potassium carbonate solution, 17 mg (0.015 mmol) of tetrakis (triphenylphosphine) palladium (0) were added to toluene 4.8. It was dissolved in ml and stirred at 80 ° C. for 4 days. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to give the desired product poly [2,7- (9,9-dihexyl-9 H -fluorene) -alt- 4,7- (benz Imidazole-2-spirocyclohexane)] to 180 mg.

Example  2

Poly [2,6- (4,4- Vis (2- Ethylhexyl )-4 H Cyclopenta [2,1-b: 3,4- b ' ] Taisai pen)- alt -4,7- ( Benzimidazole -2- Spycyclohexane )]

1) Synthesis of Di (3-cyenyl) methanol (Formula 2b)

10 g (105.55 mmol) of 3-bromosiophene (Formula 2a) was dissolved in 25 ml of tetrahydrofuran, and 69.27 ml (110.83 mmol) of 1.6 M n -butyllithium was slowly added at -78 ° C. After stirring for 10 minutes, 3.90 ml (48.56 mmol) of ethyl formate was slowly added, followed by 30 minutes of stirring at room temperature. 10 ml of distilled water was added, extracted with ether and distilled water, and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 7.98 g (77%) of a yellow solid were obtained.

R _f = 0.3 (SiO ₂ , ethyl acetate: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.31 (dd, 2H, J = 4.94, 7.97 Hz), 7.23-7.19 (m, 2H), 7.05 (dd, 2H, J = 4.94, 6.32 Hz), 5.94 ( br, 1H), 2.38 (br, 1H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 72.0, 37.4, 31.8, 29.7, 29.6, 29.5, 29.2, 25.6, 22.6, 14.1

HRMS, m / e, C ₁₇ H ₃₅ O, [MH ⁺ ] 255.2685 (calcd. 255.2688)

2) Synthesis of 3- (3-cyenylmethyl) thiophene (Formula 2c)

After dissolving 3.04 g (76.16 mmol) of lithium aluminum hydride in 30 ml of ether, a solution of 12.19 g (91.40 mmol) of aluminum (III) chloride in 30 ml of ether was added and stirred at room temperature for 10 minutes. 14.95 g (76.16 mmol) of the compound of Formula 2b was slowly added to a solution of 60 ml of ether, followed by stirring at room temperature for 2 hours. After cooling to 0 ° C., 100 ml of distilled water was added, extracted with ether and distilled water, and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 12 g (87%) of a colorless solid were obtained.

R _f = 0.45 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.29 (dd, 2H, J = 4.67, 7.97 Hz), 6.99-6.91 (m, 4H), 4.00 (s, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 141.2, 128.6, 125.8, 121.4, 31.3

HRMS, m / e, C ₉ H ₈ S ₂ , 180.0067 (calcd. 180.0067)

3) Synthesis of 2-bromo-3-[(2-bromo-3-cyenyl) methyl] thiophene (Formula 2d)

11.75 g (65.17 mmol) of the compound of Chemical Formula 2c thus obtained was dissolved in 700 ml of tetrahydrofuran, and 23.20 g (130.35 mmol) of N -bromosuccinimide was added little by little, followed by stirring at room temperature for 1 hour. The solvent was distilled under vacuum, extracted with ether and distilled water, and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 18.82 g (85%) of a colorless solid were obtained.

R _f = 0.6 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.19 (d, 2H, J = 5.49 Hz), 6.75 (d, 2H, J = 5.49 Hz), 3.86 (s, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 139.0, 128.7, 125.9, 110.1, 29.7

HRMS, m / e, C ₉ H ₆ Br ₂ S ₂ , 335.8281 (calcd. 335.8278)

4) Synthesis of 4H -cyclopenta [2,1-b: 3,4-b '] diocyphene (Formula 2e)

10 g (29.57 mmol) of the compound of Chemical Formula 2d thus obtained was dissolved in 38 ml of tetrahydrofuran, and then 36.97 ml (59.15 mmol) of 1.6M n -butyllithium was slowly added at -78 ° C, and stirred for 30 minutes. (II) 3.98 g (59.16 mmol) was slowly added to a solution dissolved in 57 ml of tetrahydrofuran and stirred at 0 ° C. for 4 hours. After 40 ml of 1 M hydrochloric acid was added, the solvent was distilled in vacuo, extracted with ether and distilled water, and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 2.58 g (49%) of a colorless liquid were obtained.

R _f = 0.5 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.19 (d, 2H, J = 4.94 Hz), 7.10 (d, 2H, J = 4.94 Hz), 3.54 (s, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 149.9, 138.9, 124.7, 123.2, 32.0

HRMS, m / e, C ₉ H ₆ S ₂ , 177.9912 (calcd. 177.9911)

5) 4,4-bis (2-ethylhexyl) -4 H - cyclopenta: Synthesis of [2,1-b 3,4-b ' ] thiophene between the die (Formula 2f)

3.91 g (21.93 mmol) of the compound of Formula 2e and 100 mg (0.44 mmol) of triethylbenzylammonium chloride were dissolved in 40 ml of dimethyl sulfoxide, and 9.03 ml (48.25 mmol) of 2-ethylhexyl bromide was added thereto. After stirring for 1.93ml (48.25mmol) of 50% sodium hydroxide was added and stirred at 80 ° C for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite and distillation of the solvent in a liquid residue produced by column chromatography to separate the product. 7.14 g (81%) of a yellow liquid were obtained.

R _f = 0.8 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.11 (d, 2H, J = 4.67 Hz), 6.94-6.88 (m, 2H), 1.94-1.77 (m, 4H), 1.08-0.80 (m, 18H), 0.75 (t, 6H, J = 6.73 Hz), 0.58 (t, 6H, J = 7.69 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.8, 137.0, 124.2, 122.5, 53.5, 43.5, 35.3, 34.4, 28.8, 27.5, 23.0, 14.3, 10.8

HRMS, m / e, C ₂₅ H ₃₈ S ₂ , 402.2411 (calcd. 402.2415)

6) 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxabolorane-2- 1) Synthesis of 4H -cyclopenta- [2,1-b: 3,4-b '] diocyphene (Formula 2g)

1.28 g (3.18 mmol) of the compound of Chemical Formula 2f and 1.43 ml (9.54 mmol) of tetramethylethylenediamine were dissolved in 21 ml of tetrahydrofuran, and 5.96 ml (9.54 mmol) of 1.6 M n -butyllithium was added at -78 ° C. After slowly adding, stirring for 30 minutes, stirring at room temperature for 1 hour, cooling to -78 ° C, and then 3.24ml of isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane (15.89 mmol) was added slowly and stirred for 30 minutes, followed by stirring at room temperature for 12 hours. After adding 1 ml of distilled water, the mixture was extracted with an aqueous solution of ether and saturated sodium bicarbonate, dried over magnesium sulfate, and the liquid residue produced by vacuum distillation of the solvent was separated by column chromatography. 1.44 g (77%) of a pale yellow liquid was obtained.

R _f = 0.2 (SiO ₂ , methylenedichloride: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.43 (t, 2H, J = 5.49 Hz), 1.92-1.76 (m, 4H), 1.34 (s, 24H), 1.00-0.50 (m, 30H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.8, 137.0, 124.2, 122.5, 53.5, 43.5, 35.3, 34.4, 28.8, 27.5, 23.0, 14.3, 10.8

HRMS, FAB ⁺ , C ₃₇ H ₆₀ B ₂ O ₄ S ₂ , 654.4124 (calcd. 654.4132)

7) poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7 -(Benzimidazole-2-spirocyclohexane)] (Formula 2h)

Thus obtained 540 mg (0.825 mmol) of the compound of formula 2g, 284 mg (0.825 mmol) of the compound of formula 1h, 4.3 ml of a 2M potassium carbonate solution, and 28.6 mg (0.025 mmol) of tetrakis (triphenylphosphine) palladium (0) were toluene. It was dissolved in 8.6ml and stirred at 80 ° C for 4 days. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1 430 mg of b: 3,4-b '] dithiophene) -alt- 4,7- (benzimidazole-2-spirocyclohexane)] were obtained.

Example  3

Poly [2,7- (9,9- Dihexyl -9 H - Fluorene ) - alt -4,7- ( Benzimidazole -2- Spirosai Clohexane-4'-ol)]

1) Synthesis of 4-hydroxycyclohexanone (Formula 3b)

After dissolving 5 g (43.04 mmol) of 1,4-cyclohexanediol (Formula 3a) in 200 ml of acetone, 17.21 ml (43.04 mmol) of 1.6 M Jones reagent was slowly added at 0 ° C., stirred for 30 minutes, and stirred at room temperature for 1 hour. It was. The solvent was distilled under vacuum, extracted with ethyl acetate and distilled water, and dried over magnesium sulfite. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 1.77 g (36%) of a colorless liquid were obtained.

R _f = 0.3 (SiO ₂ , ethyl acetate: hexane = 2: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 4.22-4.12 (m, 1H), 2.66-2.50 (m, 2H), 2.36-2.21 (m, 2H), 2.11-1.88 (m, 4H), 1.84 (br , 1H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 212.4, 66.0, 37.4, 33.8

HRMS, m / e, C ₆ H ₁₀ O ₂ , 114.0680 (calcd. 114.0681)

2) Synthesis of 4,7-dibromobenzimidazole-2 ( 3H ) -spirocyclohexane-4'-ol (Formula 3c)

2.15 g (18.80 mmol) of the compound of Formula 3b and 5 g (18.80 mmol) of the compound of Formula 1f were dissolved in 120 ml of toluene, and then stirred at 100 ° C. for 6 hours. The solvent was distilled off in vacuo and the remaining liquid residue was separated by column chromatography. 5.95 g (87%) of brown liquid was obtained.

R _f = 0.35 (SiO ₂ , Ethyl acetate: hexane = 1: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 4.22-4.12 (m, 1H), 2.66-2.50 (m, 2H), 2.36-2.21 (m, 2H), 2.11-1.88 (m, 4H), 1.84 (br , 1H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 212.4, 66.0, 37.4, 33.8

HRMS, m / e, C ₆ H ₁₀ O ₂ , 114.0680 (calcd. 114.0681)

3) Synthesis of 4,7-Dibromobenzimidazole-2-spirocyclohexane-4'-ol (Formula 3d)

5.95 g (16.43 mmol) of the compound of Formula 3c thus obtained was dissolved in 170 ml of methylene chloride, and 20.17 g (197.20 mmol) of 85% manganese dioxide (IV) was added at room temperature. After stirring for 1 hour at room temperature, the mixture was extracted with methylene chloride and distilled water and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 4.61 g (78%) of a yellow solid were obtained.

R _f = 0.4 (SiO ₂ , Ethyl acetate: hexane = 2: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.20 (s, 2H), 4.18-4.07 (m, 1H), 2.29-2.16 (m, 2H), 2.15-2.00 (m, 2H), 2.00-1.84 (m , 2H), 1.73 (br, 1H), 1.62 (br, 1H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.5, 157.4, 136.2, 136.1, 119.1, 118.8, 106.5, 68.6, 33.0, 29.6

HRMS, m / e, C ₁₂ H ₁₂ Br ₂ N ₂ O, 357.9317 (calcd. 357.9316)

4) poly [2,7- (9,9-dimethyl-hexyl -9 H - fluorenyl) - alt -4,7- (4'-benz imidazol-2-Spy cyclohexanol)] (formula 3e ) Synthesis

Thus obtained 429 mg (1.194 mmol) of the compound of Formula 3d, 700 mg (1.194 mmol) of the compound of Formula 1c, 6 ml of a 2M potassium carbonate aqueous solution and 41.4 mg (0.036 mmol) of tetrakis (triphenylphosphine) palladium (0) 5 ml of toluene It was dissolved in and stirred at 80 ° C for 4 days. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to give the desired product poly [2,7- (9,9-dihexyl-9 H -fluorene) -alt- 4,7- (benz Imidazole-2-spirocyclohexane-4'-ol)].

Example  4

Poly [2,6- (4,4- Vis (2- Ethylhexyl )-4 H Cyclopenta [2,1-b: 3,4- b ' ] Taisai pen)- alt -4,7- ( Benzimidazole -2- Spycyclohexane -4'-ol)]

1) Poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7 -(Benzimidazole-2-spirocyclohexane-4'-ol)] (Formula 4a)

470 mg (0.718 mmol) of the compound of Formula 2, 258 mg (0.718 mmol) of the compound of Formula 3d, 3.5 ml of a 2M potassium carbonate solution, and 24.9 mg (0.022 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in 5 ml of toluene. After stirring at 80 ° C for 4 days. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1 b: 3,4-b '] thiophene is two hundred forty-two) - alt -4,7- (4'-benz imidazol-2-Spy cyclohexanol) to give the 250mg.

Example  5

Poly [2,6- (4,4- Vis (2- Ethylhexyl )-4 H Cyclopenta [2,1-b: 3,4- b ' ] Daissai pen ) - co -4,7- ( Benzimidazole -2- Spycyclohexane ) - co -4,7- ( Benzimidazole -2-spirocyclohexane-4'-ol)]

1) Poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the die) -co-4,7 -(Benzimidazole-2-spirocyclohexane) -co-4,7- (benzimidazole-2-spirocyclohexane-4'-ol)] (Formula 5a)

487 mg (0.744 mmol) of the compound of formula 2g, 128 mg (0.372 mmol) of the compound of formula 1h, 134 mg (0.372 mmol) of the compound of formula 3d, 3.7 ml of an aqueous 2M potassium carbonate solution, and tetrakis (triphenylphosphine) palladium (0) 27.6 mg (0.024 mmol) was dissolved in 4.8 ml of toluene and stirred at 80 ° C. for 4 days. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1 b: 3,4-b '] diocyphene) -co-4,7- (benzimidazole-2-spirocyclohexane) -co-4,7- (benzimidazole-2-spirocyclohexane -4'-ol)] 230 mg.

Example  6

Poly [2,6- (4,4- Vis (2- Ethylhexyl )-4 H Cyclopenta [2,1-b: 3,4- b ' ] Taisai pen)- alt -4,7- ( Benzimidazole -2- spiro- (4 '-( Methoxy methoxy ) - Cyclohexane )]

1) Synthesis of 4,7-Dibromo-4 '-(methoxymethoxy) benzimidazole-2-spirocyclohexane (Formula 6b)

2 g (5.55 mmol) of the compound of Formula 3d was dissolved in 80 ml of methylene chloride, and 3.91 ml (22.22 mmol) of N , N -diisopropylamine were added at 0 ° C., followed by stirring for 5 minutes, followed by chloromethyl methyl ether (Formula 6a). 1.69ml (22.22mmol) was added slowly and stirred at 0 ° C for 1 hour and then at room temperature for 12 hours. 30 ml of saturated aqueous ammonium chloride solution was added, extracted with methylene chloride and distilled water, and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 2.25 g (100%) of a yellow solid were obtained.

R _f = 0.3 (SiO ₂ , ethyl acetate: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.20 (s, 2H), 4.77 (s, 2H), 4.04-3.94 (m, 1H), 3.43 (s, 3H), 2.27-2.05 (m, 4H), 1.95 (br, 2H), 1.68 (br, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.4, 157.2, 136.2, 136.1, 119.0, 118.8, 106.6, 95.1, 72.9, 55.5, 30.1, 29.2

HRMS, m / e, C ₁₄ H ₁₆ Br ₂ N ₂ O ₂ , 401.9582 (calcd. 401.9579)

2) poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7 Synthesis of-(benzimidazole-2-spiro- (4 '-(methoxymethoxy) -cyclohexane)] (Formula 6c)

Thus obtained 302 mg (0.749 mmol) of the compound of Formula 6b, 490 mg (0.749 mmol) of the compound of Formula 2g, 3.7 ml of a 2M potassium carbonate solution, and 25.9 mg (0.022 mmol) of tetrakis (triphenylphosphine) palladium (0) were toluene. It was dissolved in 5ml and stirred for 4 days at 80 ℃. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1 250 mg of b: 3,4-b '] diithiophene- alt- 4,7- (benzimidazole-2-spiro- (4'-(methoxymethoxy) -cyclohexane)] was obtained.

Example  7

Poly [2,6- (4,4- Vis (2- Ethylhexyl )-4 H Cyclopenta [2,1-b: 3,4- b ' ] Taisai pen)- alt -4,7- ( Benzimidazole -2- Spiro- (4 '-((2' '- Ethylhexyl ) Oxy ))- Cyclohexane )]

1) Synthesis of 1,4-dioxaspiro [4.5] decan-8-ol (Formula 7b)

5 g (32.01 mmol) of 1,4-cyclohexanedione mono-ethylene ketal (Formula 7a) was dissolved in 100 ml of methanol, and sodium borohydride 3.63 g (32.01 mmol) was added little by little at 0 ° C., followed by stirring for 10 minutes. Stir at room temperature for 3 hours. After cooling to 0 ° C., 100 ml of distilled water was added, followed by vacuum distillation. The remaining residue was extracted with ethyl acetate and distilled water, and dried over magnesium sulfate. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 4.76 g (94%) of a colorless liquid were obtained.

R _f = 0.3 (SiO ₂ , ethyl acetate: hexane = 2: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.96-3.86 (m, 4H), 3.81-3.71 (m, 1H), 2.01 (br, 1H), 1.90-1.71 (m, 4H), 1.69-1.47 (m , 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 108.5, 68.3, 64.5, 64.4, 32.2, 31.8

HRMS, m / e, C ₈ H ₁₄ O ₃ , 158.0944 (calcd. 158.0943)

2) Synthesis of 8-[(2-ethylhexyl) oxy] -1,4-dioxaspiro [4.5] decane (Formula 7c)

Dissolve 1.46 g (36.41 mmol) of sodium hydride in 72 ml of N , N -dimethylformamide and 4.8 g (30.34 mmol) of 1,4-dioxaspiro [4.5] decan-8-ol (Formula 7b) at 0 ° C. Was dissolved in 72 ml of N , N -dimethylformamide, and slowly added thereto. The mixture was stirred at 0 ° C. for 30 minutes, and then 8.52 ml (45.51 mmol) of 2-ethylhexyl bromide was added thereto, followed by stirring at room temperature for 3 hours. After cooling to 0 ° C., 10 ml of distilled water was added, followed by vacuum distillation. The remaining residue was extracted with ethyl acetate and distilled water, and dried over magnesium sulfate. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 0.52 g (6%) of a colorless liquid were obtained.

R _f = 0.25 (SiO ₂ , ethyl acetate: hexane = 1:10)

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.96-3.86 (m, 4H), 3.81-3.71 (m, 1H), 2.01 (br, 1H), 1.90-1.71 (m, 4H), 1.69-1.47 (m , 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 108.5, 68.3, 64.5, 64.4, 32.2, 31.8

HRMS, m / e, C ₈ H ₁₄ O ₃ , 158.0944 (calcd. 158.0943)

3) Synthesis of 4-[(2-ethylhexyl) oxy] cyclohexanone (Formula 7d)

0.52 g (1.92 mmol) of the compound of formula 7c thus obtained were dissolved in 5 ml of acetic acid, and stirred at 50 ° C. for 12 hours. 50 ml of saturated sodium carbonate solution was added, extracted with ethyl acetate and distilled water, and dried over magnesium sulfite. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 0.35 g (79%) of a colorless liquid were obtained.

R _f = 0.2 (SiO ₂ , Ethyl acetate: hexane = 1:10)

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.68-3.59 (m, 1H), 3.40-3.29 (m, 2H), 2.65-2.48 (m, 2H), 2.30-2.16 (m, 2H), 2.16-2.00 (m, 2H), 1.96-1.59 (m, 2H), 1.56-1.44 (m, 1H), 1.42-1.16 (m, 8H), 0.94-0.78 (m, 6H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 211.9, 72.9, 71.4, 40.2, 37.4, 30.9, 30.8, 30.7, 29.4, 24.2, 23.3, 14.3, 11.4

HRMS, m / e, C ₁₄ H ₂₆ O ₂ , 226.1931 (calcd. 226.1933)

4) Synthesis of 4,7-Dibromo-4 '-[(2-ethylhexyl) oxy] benzimidazole-2 ( 3H ) -spirocyclohexane (Formula 7e)

464 mg (1.74 mmol) of the compound of Formula 7d and 395 mg (1.74 mmol) of the compound of Formula 1f were dissolved in 11 ml of toluene, and then stirred at 100 ° C. for 6 hours. The solvent was distilled off in vacuo and the remaining liquid residue was separated by column chromatography. 558 mg (67%) of a colorless liquid were obtained.

R _f = 0.8 (SiO ₂ , ethyl acetate: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.96-3.86 (m, 4H), 3.81-3.71 (m, 1H), 2.01 (br, 1H), 1.90-1.71 (m, 4H), 1.69-1.47 (m , 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 108.5, 68.3, 64.5, 64.4, 32.2, 31.8

HRMS, m / e, C ₈ H ₁₄ O ₃ , 158.0944 (calcd. 158.0943)

5) Synthesis of 4,7-Dibromo-4 '-[(2-ethylhexyl) oxy] benzimidazole-2-spirocyclohexane (Formula 7f)

558 mg (1.18 mmol) of the compound of Chemical Formula 7e thus obtained was dissolved in 17 ml of methylene chloride, and then 1.44 g (14.11 mmol) of 85% manganese dioxide (IV) was added at room temperature. After stirring for 1 hour at room temperature, the mixture was extracted with methylene chloride and distilled water and dried over magnesium sulfite. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 513 mg (92%) of yellow liquid were obtained.

R _f = 0.45 (SiO ₂ , ethyl acetate: hexane = 1: 8)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.18 (s, 2H), 3.70-3.58 (m, 1H), 3.41-3.28 (m, 2H), 2.22-1.96 (m, 6H), 1.56-1.16 (m , 11H), 0.94-0.78 (m, 6H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.4, 157.2, 136.1, 136.0, 119.1, 119.0, 107.2, 74.7, 71.3, 40.3, 30.9, 29.6, 29.5, 29.0, 24.2, 23.3, 14.4, 11.4

HRMS, m / e, C ₂₀ H ₂₈ Br ₂ N ₂ O, 470.0566 (calcd. 470.0568)

6) poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1-b: 3,4-b '] thiophene between the dies) - alt -4,7 -(Benzimidazole-2-spiro- (4 '-((2''-ethylhexyl) oxy))-cyclohexane)] (Formula 7g)

Thus obtained 376 mg (0.796 mmol) of the compound of formula (7f), 521 mg (0.796 mmol) of the compound of formula (2g), 4 ml of 2M aqueous solution of potassium carbonate, and tetrakis (triphenylphosphine) palladium (0) 27.6 mg (0.024 mmol) were added to toluene 5.2. After dissolving in ml, the mixture was stirred at 80 ° C. for 4 days. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,6- (4,4-bis (2-ethylhexyl) -4 H - cyclopenta [2,1 b: 3,4-b '] dithiophene) -alt- 4,7- (benzimidazole-2-spiro- (4'-((2 ''-ethylhexyl) oxy))-cyclohexane) ] 200 mg was obtained.

Example  8

Poly [5,5 '-(3,3'- Dihexyloxy -(2,2'- Baissaifen ))- alt -4,7- ( Benzimidazole -2-s Pyrocyclohex Acid)]

1) Synthesis of 3- (hexyloxy) thiophene (Formula 8b)

6.33 g (158.33 mmol) of sodium hydride was dissolved in 25 ml of N , N -dimethylformamide, and 66.43 ml (527.78 mmol) of 1-hexanol was slowly added at 0 ° C. After stirring for 2 hours at room temperature, 2.05 g (10.56 mmol) of copper iodide (I) and 10 g (105.56 mmol) of 3-bromosiophene (formula 8a) were added thereto. After stirring for 1 hour at 100 ° C, 2.05 g (10.56 mmol) of copper iodide was further added, followed by stirring for 12 hours. After cooling to 0 ° C., 10 ml of distilled water was added, followed by vacuum distillation. The remaining residue was extracted with ethyl acetate and distilled water, and dried over magnesium sulfate. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 18.61 g (96%) of a colorless liquid were obtained.

R _f = 0.25 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.19 (dd, 1H, J = 3.02, 5.22 Hz), 6.77 (dd, 1H, J = 1.65, 5.22 Hz), 6.24 (dd, 1H, J = 1.65, 3.02 Hz), 1.84-1.51 (m, 2H), 1.52-1.40 (m, 2H), 1.40-1.25 (m, 4H), 0.92 (t, 3H, J = 6.87 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 158.0, 124.4, 119.4, 96.8, 70.1, 31.5, 29.2, 25.7, 22.5, 14.0

HRMS, m / e, C ₁₀ H ₁₆ OS, 184.0920 (calcd. 184.0922)

2) Synthesis of 2-bromo-3- (hexyloxy) thiophene (Formula 8c)

5 g (27.13 mmol) of the compound of Chemical Formula 8b thus obtained was dissolved in 60 ml of N , N -dimethylformamide, and then blocked with light, followed by addition of 4.83 g (27.13 mmol) of N -bromosuccinimide, followed by 3 at room temperature. Stirred for time. The solvent was evaporated in vacuo and the residue was extracted with ether and saturated aqueous sodium bicarbonate solution and dried over magnesiumsulfite. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 7.01 g (98%) of a pale yellow liquid was obtained.

R _f = 0.6 (SiO ₂ , ethyl acetate: hexane = 1:20)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.20 (d, 1H, J = 6.04 Hz), 6.76 (d, 1H, J = 5.77 Hz), 4.06 (t, 2H, J = 6.59 Hz), 1.82-1.68 (m, 2H), 1.54-1.40 (m, 2H), 1.40-1.28 (m, 4H), 0.94 (t, 3H, J = 6.87 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 154.4, 124.0, 117.4, 91.3, 72.1, 31.4, 29.3, 25.4, 22.5, 13.9

HRMS, m / e, C ₁₀ H ₁₆ OS, 184.0920 (calcd. 184.0922)

3) 3,3'-dihexyloxy- [2,2'-bithiophene] (Formula 8d)

Dissolve 1.27 g (52.31 mmol) of magnesium in 10 ml of tetrahydrofuran, and then slowly add 3.44 g (13.08 mmol) of 2-bromo-3- (hexyloxy) thiophene (Formula 8c) at room temperature, and then add 3 Stirred for time. 3.44 g (13.08 mmol) of 2-bromo-3- (hexyloxy) thiophene (Formula 8c) was dissolved in 15 ml of tetrahydrofuran, and slowly added thereto, followed by stirring for 12 hours. The solvent was evaporated in vacuo and the residue was extracted with ether and saturated aqueous sodium bicarbonate solution and dried over magnesiumsulfite. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 1.6 g (33%) of a yellow solid were obtained.

R _f = 0.2 (SiO ₂ , methylene chloride: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.11 (d, 2H, J = 5.49 Hz), 6.87 (d, 2H, J = 5.49 Hz), 4.14 (t, 4H, J = 6.59 Hz), 1.94-1.80 (m, 4H), 1.63-1.48 (m, 4H), 1.46-1.29 (m, 8H), 0.98 (t, 6H, J = 6.87 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 152.2, 121.8, 116.3, 114.4, 72.2, 31.9, 30.0, 26.0, 22.9, 14.3

HRMS, m / e, C ₂₀ H ₃₀ O ₂ S ₂ , 366.1686 (calcd. 366.1687)

4) 5,5'-di (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) -3,3'-dihexyloxy- [2,2 ' -Biothiophene] (Formula 8e)

1 g (2.73 mmol) of the compound of Formula 8d and 1.23 ml (8.18 mmol) of tetramethylethylenediamine were dissolved in 25 ml of tetrahydrofuran, and 5.11 ml (8.18 mmol) of 1.6 M n -butyllithium was slowly added at -78 ° C. After addition, the mixture was stirred for 30 minutes, stirred at room temperature for 1 hour, cooled to -78 ° C, and then 2.84ml (13.64mmol) of isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane ) Was added slowly and stirred for 30 minutes, followed by stirring at room temperature for 12 hours. After adding 1 ml of distilled water, the mixture was extracted with an aqueous solution of ether and saturated sodium bicarbonate, dried over magnesium sulfate, and the liquid residue produced by vacuum distillation of the solvent was separated by column chromatography. 1.16 g (68%) of a yellow solid were obtained.

R _f = 0.1 (SiO ₂ , methylene chloride: hexane = 1: 4)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.11 (d, 2H, J = 5.49 Hz), 6.87 (d, 2H, J = 5.49 Hz), 4.14 (t, 4H, J = 6.59 Hz), 1.94-1.80 (m, 4H), 1.63-1.48 (m, 4H), 1.46-1.29 (m, 8H), 0.98 (t, 6H, J = 6.87 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 152.2, 121.8, 116.3, 114.4, 72.2, 31.9, 30.0, 26.0, 22.9, 14.3

HRMS, m / e, C ₂₀ H ₃₀ O ₂ S ₂ , 366.1686 (calcd. 366.1687)

5) Poly [5,5 '-(3,3'-dihexyloxy- (2,2'-bithiophene))- alt- 4,7- (benzimidazole-2-spirocyclohexane) ] (Formula 8f)

Thus obtained 485 mg (0.784 mmol) of the compound of Formula 8e, 270 mg (0.784 mmol) of the compound of Formula 1h, 4 ml of an aqueous solution of 2M potassium carbonate and tetrakis (triphenylphosphine) palladium (0) 27.2 mg (0.024 mmol) were added to toluene 4.9. After dissolving in ml, the mixture was stirred at 80 ° C. for 4 days. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [5,5 '-(3,3'-dihexyloxy- (2,2'-bithiophene)). 200 mg of alt- 4,7- (benzimidazole-2-spirocyclohexane)] was obtained.

Example  9

Poly [2,7- (9- (1'- Octylnonyl ) -9 H - Carbazole ) - alt -5,5- (4 ', 7'- die (Cyen-2-yl)- Ben Zimidazole-2'- Spycyclohexane )]

1) Synthesis of Heptadecan-9-ol (Formula 9b)

2.17 ml (27.00 mmol) of ethyl formate (Formula 9a) was dissolved in 40 ml of tetrahydrofuran, and 40.50 ml (80.99 mmol) of 2M octyl magnesium bromide was slowly added at −78 ° C., followed by stirring at room temperature for 12 hours. After adding 10 ml of methanol, the mixture was extracted with ethyl acetate and saturated aqueous ammonium chloride solution, dried over magnesium sulfate, and the solid residue produced by vacuum distillation of the solvent was separated by column chromatography. 5.25 g (76%) of a white solid were obtained.

R _f = 0.2 (SiO ₂ , Ethyl acetate: hexane = 1:10)

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.57 (br, 1H), 1.50-1.35 (m, 4H), 1.34-1.20 (m, 24H), 0.87 (t, 6H, J = 6.72, 6.72 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 72.0, 37.4, 31.8, 29.7, 29.6, 29.5, 29.2, 25.6, 22.6, 14.1

HRMS, m / e, C ₁₇ H ₃₅ O, [MH ⁺ ] 255.2685 (calcd.255.2688)

2) Synthesis of 1-octylnonyl 4-methylbenzenesulfonate (Formula 9c)

10 g (38.99 mmol) of the compound of Formula 9b, 14.13 ml (101.38 mmol) of triethylamine, and 3.73 g (38.99 mmol) of triethylamine hydrochloride were dissolved in 40 ml of methylene chloride, and p -toluenesulfonyl chloride was obtained at 0 ° C. 9.66 g (50.69 mmol) was dissolved in 40 ml of methylene chloride and stirred for 2 hours after addition. After adding 50 ml of distilled water, the mixture was extracted with methylene chloride and distilled water, dried over magnesium sulfite, and the solid residue formed by vacuum distillation of the solvent was separated through column chromatography. 15.6 g (97%) of a white solid were obtained.

R _f = 0.4 (SiO ₂ , Ethyl acetate: hexane = 1:10)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.80 (d, 2H, J = 8.5 Hz), 7.33 (d, 2H, J = 8.5 Hz), 4.53 (q, 1H, J = 6.0 Hz), 2.44 (s , 3H), 1.62-1.40 (m, 4H), 1.36-0.98 (m, 24H), 0.88 (t, 6H, J = 6.87, 6.87)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 144.5, 135.0, 129.8, 127.9, 84.9, 34.3, 32.1, 29.6, 29.5, 29.4, 24.9, 22.9, 21.8, 14.3

HRMS, FAB ⁺ , C ₂₄ H ₄₂ O ₃ S, 411.2929 (calcd. 411.2933)

3) Synthesis of 4,4,5,5-tetramethyl-2- (2'-cyenyl) -1,3,2-dioxaborolane (Formula 9e)

After dissolving 10 g (118.85 mmol) of thiophene (Formula 9d) in 150 ml of tetrahydrofuran, 96.57 ml (154.50 mmol) of 1.6M n -butyllithium was slowly added at -78 ° C, stirred for 30 minutes, and stirred at room temperature for 1 hour. After cooling to -78 ° C, 48.49ml (237.70mmol) of isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane was added slowly and stirred for 30 minutes, followed by 12 at room temperature. Stirred for time. 10 ml of distilled water was added thereto, extracted with an aqueous solution of ether and saturated sodium bicarbonate, dried over magnesium sulfate, and the solid residue formed by vacuum distillation of the solvent was separated by column chromatography. 21.04 g (84%) of a white solid were obtained.

R _f = 0.6 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.68-7.60 (m, 2H), 7.21 (dd, 1H, J = 4.67, 3.29 Hz), 1.34 (s, 12H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 137.4, 132.6, 128.5, 84.3, 25.0

HRMS, m / e, C ₁₀ H ₁₅ BO ₂ S, 210.0888 (calcd. 210.0888)

4) Synthesis of 4,7-di (cyen-2'-yl) -benzimidazole-2-spirocyclohexane (Formula 9f)

Thus obtained 8.98 g (42.73 mmol) of the compound of formula 9e, 4.2 g (12.21 mmol) of the compound of formula 1h, 61.04 ml of a 2M potassium carbonate solution, and 1.41 g (1.22 mmol) of tetrakis (triphenylphosphine) palladium (0) Was dissolved in 42 ml of toluene and stirred at 80 ° C. for 12 hours. Extraction with ethyl acetate and distilled water, drying with magnesium sulfite and distilling off the solvent under vacuum distilled the solid residue from the product by column chromatography. 2.15 g (50%) of a red solid were obtained.

R _f = 0.4 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.09 (dd, 2H, J = 4.95, 3.84 Hz), 7.39 (dd, 2H, J = 6.31, 5.22 Hz), 7.33 (s, 2H), 7.15 (dd, 2H, J = 8.79, 5.22 Hz), 2.12-1.98 (m, 4H), 1.88-1.70 (m, 6H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.9, 139.1, 128.8, 128.4, 128.3, 128.2, 127.0, 108.2, 33.6, 26.2, 25.4

HRMS, m / e, C ₂₀ H ₁₈ N ₂ S ₂ , 550.2694 (calcd. 550.2688)

5) Synthesis of 4,7-di (2'-bromocyen-5'-yl) -benzimidazole-2-spirocyclohexane (Formula 9g)

500 mg (1.43 mmol) of the compound of Formula 9f thus obtained were dissolved in 12 ml of chloroform, blocked light, and then 508 mg (2.85 mmol) of N -bromosuccinimide was added thereto, followed by stirring at room temperature for 3 hours. Extracted with chloroform and distilled water and dried over magnesium sulfite. The product was separated by column chromatography of the liquid residue which is produced after vacuum distillation of the solvent. 1.18 g (83%) of a red solid were obtained.

R _f = 0.6 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.71 (d, 2H, J = 3.85 Hz), 7.23 (s, 2H), 7.09 (d, 2H, J = 4.12 Hz), 2.10-1.94 (m, 4H) , 1.88-1.77 (m, 2H), 1.76-1.64 (m, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.4, 140.2, 130.9, 128.2, 127.6, 127.5, 115.5, 108.7, 33.4, 26.0, 25.3

HRMS, m / e, C ₂₀ H ₁₆ Br ₂ N ₂ S ₂ , 507.9109 (calcd. 507.9101)

6) Synthesis of 4,4'-Dibromo-2-nitro-1,1'-biphenyl (Formula 9i)

10 g (32.05 mmol) of 4,4'-dibrobiphenyl (9h) was dissolved in 150 ml of acetic acid, and then 50.48 ml (801.23 mmol) of nitric acid and 5 ml of distilled water were slowly added at 100 ° C. After stirring for 30 minutes, the first precipitate formed was dissolved again, cooled to room temperature, and the yellow solid formed was filtered and recrystallized with ethanol. 10.88 g (95%) of a yellow solid were obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.05 (d, 1H, J = 1.92 Hz), 7.79 (dd, 1H, J = 8.24, 10.44 Hz), 7.59 (d, 2H, J = 8.24 Hz), 7.32 (d, 1H, J = 8.52 Hz), 7.18 (d, 2H, J = 8.24 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 149.5, 135.8, 135.5, 134.3, 133.3, 132.3, 129.7, 127.5, 123.3, 122.1

HRMS, m / e, C ₁₂ H ₇ Br ₂ NO ₂ , 356.8830 (calcd. 356.8824)

7) Synthesis of 2,7-Dibromo-9 H -carbazole (Formula 9j)

10.8 g (32.25 mmol) of the compound of formula 9i and 40.21 ml (242.02 mmol) of triethyl phosphite were stirred at 150 ° C. for 12 hours, cooled to 0 ° C., acidified with 5N aqueous hydrochloric acid solution, and then 50% aqueous sodium hydroxide solution. Neutralized. Extraction with ethyl acetate and distilled water, drying with magnesium sulfite and distilling off the solvent under vacuum distilled the solid residue from the product by column chromatography. 4.68 g (48%) of a white solid were obtained.

R _f = 0.2 (SiO ₂ , methylene chloride: hexane = 1: 2)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.07 (br, 1H), 7.91 (d, 2H, J = 8.79 Hz), 7.59 (d, 2H, J = 1.10 Hz), 7.38 (dd, 2H, J = 8.24, 9.89 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 140.5, 123.4, 122.0, 121.7, 119.9, 114.1

HRMS, m / e, C ₁₂ H ₇ Br ₂ N, 322.8947 (calcd. 322.8945)

Synthesis of carbazole (formula 9k) - 8) 2,7- dibromo-9- (1'-octyl-nonyl) -9 H

3.6 g (11.08 mmol) of the compound of formula 9j and 3.11 g (55.38 mmol) of potassium hydroxide were dissolved in 30 ml of dimethyl sulfoxide, followed by 7.28 g of 1-octynonyl 4-methylbenzenesulfonate (Formula 9c) at room temperature. 17.72 mmol) was added slowly and stirred for 6 hours. The product was separated by column chromatography, extracting with hexane and distilled water, drying with magnesium sulfite and distilling off the solvent in vacuo. 3.87 g (68%) of a white solid were obtained.

R _f = 0.5 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.90 (br, 2H), 7.69 (br, 1H), 7.53 (br, 1H), 7.34 (br, 2H), 4.48-3.32 (m, 1H), 2.28- 2.08 (m, 2H), 1.98-1.80 (m, 2H), 1.32-0.88 (m, 24H), 0.83 (t, 6H, J = 6.86 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 143.13, 139.67, 122.54, 121.69, 121.45, 121.08, 119.99, 119.40, 114.75, 112.378, 57.18, 33.70, 31.96, 29.49, 29.34, 26.95, 22.83, 14.30

HRMS, m / e, C ₂₉ H ₄₁ Br ₂ N, 561.1607 (calcd. 561.1606)

9) 9- (1-octylnonyl) -2,7-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxaborolan-2'-yl ) -9 H - synthesis of carbazole (formula 9l)

Thus obtained compound 3g (5.32 mmol) of the formula 9k was dissolved in 50 ml of tetrahydrofuran, and slowly added 1.6M n -butyllithium 7.65 ml (12.25 mmol) at -78 ° C, and stirred for 1 hour, followed by isopropoxy-4, 4.26 ml (15.97 mmol) of 4,5,5-tetramethyl [1,3,2] dioxaborolane was added thereto, followed by stirring for 1 hour, followed by stirring at room temperature for 12 hours. After adding 10 ml of distilled water, the mixture was extracted with ether and distilled water, dried over magnesium sulfite, and the solid residue produced by vacuum distillation of the solvent was separated through column chromatography. 2.77 g (79%) of a white solid were obtained.

R _f = 0.3 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.12 (t, 2H, J = 8.24 Hz), 8.09 (s, 1H), 7.88 (s, 1H), 7.67 (d, 2H, J = 7.69 Hz), 4.80 -4.46 (m, 1 H), 2.45-2.20 (m, 2 H); 2.05-1.85 (m, 2 H); 1.39 (s, 24H), 1.28-1.04 (m, 24H), 0.81 (t, 6H, J = 6.87 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 142.16, 138.91, 126.26, 124.87, 120.254, 119.96, 118.32, 115.66, 83.92, 56.59, 34.05, 32.00, 29.71, 29.55, 29.44, 27.00, 25.17, 22.83, 14.30

HRMS, m / e, C ₄₁ H ₆₅ B ₂ NO ₄ , 657.5096 (calcd. 657.5114)

10) poly [2,7- (9- (1'-octyl-nonyl) -9 H-carbazole) - alt -5,5- (4 ', 7'- die (yen between 2-yl) benzamide Imidazole-2'-spirocyclohexane)] (Formula 9m)

Thus obtained 306 mg (0.465 mmol) of the compound of formula 9l, 237 mg (0.465 mmol) of the compound of formula 9g, 2.3 ml of a 2M aqueous solution of potassium carbonate, and 16.1 mg (0.014 mmol) of tetrakis (triphenylphosphine) palladium (0) were toluene. It was dissolved in 8ml and stirred for 4 days at 80 ℃. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,7- (9- (1'-octyl-nonyl) -9 H - carbazole) - alt -5,5 -(4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane)] 360 mg.

Example  10

Poly [2,7- (9- (1'- Octylnonyl ) -9 H - Carbazole ) - alt -5,5- (4 ', 7'- die (Cyen-2-yl)- Ben Zimidazole-2'-Spiro-4 ''-((2 '' '- Ethylhexyl ) Oxy ) - Cyclohexane )] Synthesis

1) 4,7-di (cyen-2'-yl) -benzimidazole-2-spiro-4 ''-[(2 '' '-ethylhexyl) oxy] -cyclohexane (Formula 10a) synthesis

4,4,5,5-tetramethyl-2- (2'-cyenyl) -1,3,2-dioxaborolane (9e) 2.15 g (10.21 mmol) and 4,7-dibromo-4 965 mg (2.04 mmol) of '-[(2-ethylhexyl) oxy] benzimidazole-2-spirocyclohexane (Formula 7f), 10.21 ml of 2M potassium carbonate solution and tetrakis (triphenylphosphine) palladium (0) 236 mg (0.20 mmol) was dissolved in 15 ml of toluene and stirred at 80 ° C. for 12 hours. Extraction with ethyl acetate and distilled water, drying with magnesium sulfite and distilling off the solvent under vacuum distilled the solid residue from the product by column chromatography. 0.82 g (84%) of red liquid was obtained.

R _f = 0.4 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.15 (dd, 1H, J = 3.85, 4.95 Hz), 8.06 (dd, 1H, J = 3.85, 4.95 Hz), 7.40-7.34 (m, 2H), 7.31 ( s, 2H), 7.16-7.10 (m, 2H), 3.76-3.65 (m, 1H), 3.52-3.39 (m, 2H), 3.32-2.10 (m, 5H), 1.66-1.28 (m, 12H), 0.95 (t, 6H, J = 7.42 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 158.2, 158.1, 139.0, 139.0, 128.9, 128.7, 128.6, 128.5, 128.4, 128.3, 128.2, 128.0, 126.9, 126.8, 107.6, 76.0, 71.6, 40.2, 30.9, 30.4 , 30.2, 29.4, 24.2, 23.4, 14.4, 11.4

HRMS, m / e, C ₂₈ H ₃₄ N ₂ OS ₂ , 478.2109 (calcd. 478.2113)

2) 4,7-di (2'-bromosien-5'-yl) -benzimidazole-2-spiro-4 ''-[(2 '' '-ethylhexyl) oxy] -cyclohexane ( Formula 10b)

Thus, 711 mg (1.49 mmol) of the compound of Formula 10a was dissolved in 18 ml of chloroform, light was blocked, and 449 mg (2.52 mmol) of N -bromosuccinimide was added thereto, followed by stirring at room temperature for 3 hours. Extracted with chloroform and distilled water and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 863 mg (91%) of a red solid were obtained.

R _f = 0.4 (SiO ₂ , methylene chloride: hexane = 1: 2)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.76 (d, 1H, J = 4.12 Hz), 7.67 (d, 1H, J = 4.12 Hz), 7.20 (d, 2H, J = 1.10 Hz), 7.08 (d , 2H, J = 4.12 Hz), 3.76-3.65 (m, 1H), 3.50-3.39 (m, 2H), 2.30-2.06 (m, 5H), 1.64-1.22 (m, 12H), 1.00-0.84 (m , 6H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 157.7, 157.6, 140.1, 131.0, 130.8, 128.2, 128.0, 127.8, 127.7, 127.4, 115.5, 115.4, 108.1, 75.8, 71.7, 40.2, 30.9, 30.3, 30.0, 29.4 , 24.2, 23.4, 14.4, 11.4

HRMS, m / e, C ₂₈ H ₃₂ Br ₂ N ₂ OS ₂ , 634.0321 (calcd. 634.0323)

3) poly [2,7- (9- (1'-octyl-nonyl) -9 H-carbazole) - alt -5,5- (4 ', 7'- die (yen between 2-yl) benzamide Imidazole-2'-spiro-4 ''-((2 '''-ethylhexyl) oxy) -cyclohexane)] (Formula 10c)

387 mg (0.608 mmol) of the compound of Formula 10b, 400 mg (0.608 mmol) of the compound of Formula 9l, 3 ml of a 2M potassium carbonate solution and 21 mg (0.018 mmol) of tetrakis (triphenylphosphine) palladium (0) were added to 8 ml of toluene. After melting, the mixture was stirred at 80 ° C. for 4 days. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product was poly [2,7- (9- (1'-octyl-nonyl) -9 H - carbazole) - alt -5,5 -(4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spiro-4''-((2'''-ethylhexyl) oxy) -cyclohexane)] 350 mg Got.

Example  11

Poly [(2,6- (4,4- Vis (2'- Ethylhexyl )-4 H Cyclopenta [ def ] Phenanthrene))- alt -(5,5- (4 ', 7'-di (cyen-2-yl)- Benzimidazole -2'- Spycyclohexane Manufacture of))]

1) Synthesis of 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 11b)

1 g (5.3 mmol) of 4 H -cyclopenta [ def ] phenanthrene (Formula 11a) and 0.5 g of 10% palladium / carbon were dissolved in 20 ml of methanol, followed by stirring at room temperature for 20 hours under hydrogen gas. After filtering off the catalyst, the solid residue produced by vacuum distillation of the solvent was separated by column chromatography. 0.9 g (87%) of a white solid was obtained.

R _f = 0.8 (SiO ₂ , hexane100%)

FT-IR (KBr, cm ^-1 ): 3043, 3017, 2925, 2888, 2830, 2830, 1452, 1432, 1389, 810, 767, 726, 693

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.37 (d, 2H, J = 7.4 Hz), 7.24 (t, 2H, J = 7.4 Hz), 7.17 (d, 2H, J = 7.4 Hz), 3.92 (s , 2H), 3.18 (s, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 140.67, 139.65, 130.76, 127.51, 124.92, 122.95, 37.69, 26.51

HRMS, m / e, C ₁₅ H ₁₂ , 192.0943 (calcd. 192.0939)

2) Synthesis of 2,6-Dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 11c)

0.9 g (4.59 mmol) of the compound of Formula 11b thus obtained were dissolved in 80 ml of carbon tetrachloride, and then 11.67 g of aluminum dibromide complex was added, followed by stirring at 80 ° C. for 5 hours. After filtering the solids, the solid residue resulting from vacuum distillation of the solvent was separated by column chromatography. 1.52 g (93%) of a pale yellow solid was obtained.

R _f = 0.5 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 2925, 2894, 2828, 1574, 1433, 1411, 1394, 1065, 861, 839, 788

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.47 (s, 2H), 7.46 (s, 2H), 3.83 (s, 2H), 3.08 (s, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 141.81, 137.56, 131.91, 128.43, 126.43, 121.33, 37.35, 25.95

HRMS, m / e, C ₁₅ H ₁₀ Br ₂ , 347.9153 (calcd. 347.9149)

3) Synthesis of 2,6-Dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 11d)

1.52 g (4.34 mmol) of the compound of Formula 11c thus obtained was dissolved in 30 ml of carbon disulfide, and 0.27 ml (5.21 mmol) of bromine was slowly added at room temperature for 2 hours, followed by stirring for 1 hour. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 1.2 g (80%) of a pale yellow solid was obtained.

R _f = 0.53 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3043, 2926, 1570, 1419, 1403, 1309, 1211, 1063, 863, 831, 808, 711, 688

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.99 (s, 2H), 7.80 (s, 2H), 7.75 (s, 2H), 4.32 (s, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 143.03, 132.91, 128.97, 127.97, 126.41, 125.62, 125.31, 37.16

HRMS, m / e, C ₁₅ H ₈ Br ₂ , 345.8993 (calcd. 345.8993)

Synthesis of the cyclopenta [def] phenanthrene (Chemistry learning 11e) - 4) 2,6- dibromo-4,4-bis (2-ethylhexyl) -4 H

3.12 g (8.98 mmol) of the compound of formula (11d) thus obtained and a catalytic amount of triethylbenzylammonium chloride were dissolved in 175 ml of dimethyl sulfoxide, followed by addition of 4.79 ml (27.00 mmol) of 2-ethylhexyl bromide. After stirring at 60 ° C. for 1 hour, 10 ml of 50% aqueous sodium hydroxide solution was added and stirred at room temperature for 5 hours. Excess ethyl acetate was added to form sodium hydroxide precipitate, which was then filtered and the organic layer was extracted with distilled water. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 3.59 g (69.8%) of white crystals were obtained.

R _f = 0.6 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3046, 2959, 2926, 2872, 2858, 2728, 1909, 1744, 1593, 1577, 1460, 1416, 1390, 1379, 1367, 1306, 1222, 1213, 1066

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.95 (s, 2H), 7.74 (s, 2H), 7.64 (s, 2H), 2.17 (d, 4H, J = 5.1 Hz), 0.87-0.47 (m, 30H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 150.97, 135.44, 128.64, 125.89, 125.63, 124.68, 121.84, 59.72, 44.03, 35.45, 34.06, 28.28, 27.55, 22.86, 14.20, 10.53

HRMS, m / e, C ₃₁ H ₄₀ ⁷⁹ Br ⁷⁹ Br, 570.1532 (calcd. 570.1497), C ₃₁ H ₄₀ ⁷⁹ Br ⁸¹ Br, 572.1495 (calcd. 572.1476), C ₃₁ H ₄₀ ⁸¹ Br ⁸¹ Br, 574.1454 (calcd 574.1456)

5) 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxaborene-2' Synthesis of -H ) -4H-cyclopenta [ def ] phenanthrene (Formula 11f)

2.19 g (3.83 mmol) of the compound of formula 11e, 4.86 g (19.15 mmol) of bis (pinacolato) diborone, and 2.26 g (22.98 mmol) of potassium acetate were dissolved in 40 ml of N , N -dimethylformamide. 180 mg (0.23 mmol) of 1,1′-bis (diphenylphosphino) ferrocenepalladium (II) dichloro dichloromethane complex at room temperature were added, followed by stirring at 60 ° C. for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite, and distilling off the solvent under vacuum distilled off the product, the product was separated by column chromatography. 2.0 g (78%) of white crystals were obtained.

R _f = 0.42 (SiO ₂ , ethyl acetate: hexane = 1:20)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.31 (s, 2H), 7.98 (s, 0.5H by chirality of 2H), 7.96 (s, 1H by chirality of 2H), 7.94 (s, 0.5H by chirality of 2H), 2.16 (d, 4H, J = 4.67 Hz), 1.41 (s, 24H), 0.82-0.44 (m, 30H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 149.19, 139.71, 130.79, 128.23, 127.91, 126.04, 125.71, 83.91, 59.04, 44.03, 35.41, 33.98, 28.18, 27.73, 25.14, 22.90, 14.27, 10.61

HRMS, m / e, C ₄₃ H ₆₄ B ₂ O ₄ , 666.4996 (calcd. 666.5005)

6) Poly [(2,6- (4,4-bis (2'-ethylhexyl) -4 H - cyclopenta [def] phenanthrene)) - alt - (5,5- ( 4 ', 7'- Di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane))] (Formula 11g)

Thus obtained 285 mg (0.428 mmol) of the compound of Formula 11f, 217 mg (0.428 mmol) of the compound of Formula 9g, 2.1 ml of an aqueous 2M potassium carbonate solution and 14.8 mg (0.013 mmol) of tetrakis (triphenylphosphine) palladium (0) After dissolving in 11ml and stirred for 4 days at 80 ℃. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product poly [(2,6- (4,4-bis (2'-ethylhexyl) -4 H - cyclopenta [def] Phenanthrene))- alt- (5,5- (4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane))]] was obtained.

Example  12

Poly [(2,6- (4,4- Vis (4 '-((2' '- Ethylhexyl ) Oxy ) Phenyl )-4 H Cyclopenta [ def ] Phenanthrene))- alt -(5,5- (4 ', 7'- die (Cyen-2-yl)- Benzimidazole -2'- Spycyclohex Acid))]

1) Synthesis of 2,6-Dibromo- 4H -cyclopenta [ def ] phenanthren-4-one (Formula 12a)

1.2 g (3.45 mmol) of 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 11d) was dissolved in 100 ml of benzene, and 5 g (57.5 mmol) of 85% manganese dioxide (IV) was added thereto at 80 ° C. Stir for 12 hours. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 1 g (80%) of a yellow solid was obtained.

R _f = 0.2 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3442, 1720, 1628, 1454, 1417, 1218, 1066, 881, 773, 678

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.10 (s, 2H), 7.90 (s, 2H), 7.72 (s, 2H)

¹³ C NMR (75 MHz, Benzene-d6) δ 190.08, 137.89, 133.97, 129.52, 126.79, 126.72, 125.14, 124.27

HRMS, m / e, C ₁₅ H ₆ ⁷⁹ Br ⁷⁹ BrO, 359.8781 (calcd. 359.8785)

Synthesis of the cyclopenta [def] phenanthrene (Formula 12b) - 2) 2,6- dibromo-4,4-bis (4'-hydroxyphenyl) -4 H

Thus obtained 1 g (2.78 mmol) of the compound of Formula 12a, 20 ml of phenol and 0.76 g (5.56 mmol) of zinc chloride (II) were injected with hydrochloric acid gas at 50 ° C. for 3 hours, and the product was separated by column chromatography. 1.24 g (84%) of a white solid were obtained.

R _f = 0.2 (SiO ₂ , ethyl acetate: hexane = 1: 3)

FT-IR (KBr, cm ^-1 ): 3853, 3648, 3277, 3032, 1574, 1508, 1230, 1066, 899, 858, 762, 707

¹ H NMR (300 MHz, Acetone-d6) δ 8.35 (s, 2H, OH), 8.15 (d, 2H, J = 1.2 Hz), 8.00 (s, 2H), 7.80 (d, 2H, J = 1.2 Hz ), 7.10 (d, 2H, J = 4.4 Hz), 7.09 (d, 2H, J = 8.9 Hz), 6.75 (d, 2H, J = 4.4 Hz), 6.74 (d, 2H, J = 8.9 Hz)

¹³ C NMR (75 MHz, Acetone-d6) δ 157.49, 153.05, 135.54, 134.48, 130.11, 129.84, 127.16, 126.84, 126.69, 122.75, 116.22, 68.56

HRMS, m / e, C ₂₇ H ₁₆ ⁷⁹ Br ⁷⁹ BrO ₂ , 529.9518 (calcd. 529.9517)

Synthesis of the cyclopenta [def] phenanthrene (formula 12c) - 3), 2,6- dibromo-4,4-bis (4 '- ((2''- ethylhexyl) oxy) phenyl) -4 H

1.24 g (2.33 mmol) of the compound of Formula 12b thus obtained was dissolved in 100 ml of acetone, and 0.35 g (2.33 mmol) of sodium iodide, 4.93 g (1.40 mmol) of cesium carbonate, and 1.66 ml (9.32 mmol) of 2-ethylhexyl bromide were added thereto. After stirring at 70 ℃ for 24 hours. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 0.46 g (26%) of a white solid was obtained.

R _f = 0.74 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3750, 2960, 2930, 2850, 1610, 1580, 1510, 1470, 1410, 1300, 1280, 1170, 1030, 854, 764, 729

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.98 (s, 2H), 7.79 (s, 2H), 7.66 (s, 2H), 7.12 (d, 4H, J = 8.8 Hz), 6.78 (d, 4H, J = 8.8 Hz), 3.78 (d, 4H, J = 5.8 Hz), 1.65-1.69 (m, 4H), 1.25-1.51 (m, 24H), 0.85-0.91 (m, 16H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 158.78, 151.89, 135.71, 134.08, 129.27, 129.11, 126.51, 126.15, 125.95, 122.46, 114.64, 70.57, 67.76, 39.58, 30.72, 29.29, 24.13, 23.26, 14.30, 11.33

HRMS, m / e, C ₄₃ H ₄₈ ⁷⁹ Br ⁷⁹ BrO ₂ , 754.2000 (calcd. 754.2021)

4) 4,4-bis (4-((2-ethylhexyl) oxy) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2 '- synthesis of cyclopenta [def] phenanthrene (formula 12d) - dioxane Sabo Lauren-2'-yl) -4 H

0.72 g (0.95 mmol) of Bis (pinacolato) diboron and 0.47 g (4.8 mmol) of potassium acetate were dissolved in 40 ml of N , N -dimethylformamide. 50 mg (0.05 mmol) of 1,1′-bis (diphenylphosphino) ferrocenepalladium (II) dichloro dichloromethane complex was added at room temperature, followed by stirring at 60 ° C. for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite and distillation of the solvent in a liquid residue produced by column chromatography to separate the product. 0.7 g (87%) of a yellow liquid were obtained.

R _f = 0.36 (SiO ₂ , ethyl acetate: hexane = 1:20)

FT-IR (KBr, cm ^-1 ): 3744, 2914, 2852, 1617, 1521, 1469, 1381, 1328, 1245, 1130, 1020, 951, 841, 718, 525

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.37 (s, 2H), 8.00 (s, 2H), 7.86 (s, 2H), 7.23 (d, 4H, J = 9 Hz), 6.77 (d, 4H, J = 8.8 Hz), 3.79 (d, 4H, J = 5.7 Hz), 1.64-1.70 (m, 2H), 1.27-1.50 (m, 40H), 0.84-0.93 (m, 12H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 158.29, 150.47, 138.30, 137.23, 131.43, 129.59, 128.55, 127.43, 126.08, 114.30, 84.08, 70.51, 67.59, 39.62, 30.76, 29.31, 25.21, 24.09, 23.29, 14. , 11.35

HRMS, m / e, C ₅₅ H ₇₂ Br ₂ O ₆ , 850.5507 (calcd. 850.5515)

5) Poly [(2,6- (4,4-bis (4 '- ((2''- ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene)) - alt - (5 , 5- (4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane))] (Formula 12e)

Thus obtained 322 mg (0.378 mmol) of the compound of formula 12d, 192 mg (0.378 mmol) of the compound of formula 9g, 1.9 ml of 2M potassium carbonate aqueous solution, and 13.1 mg (0.011 mmol) of tetrakis (triphenylphosphine) palladium (0) were toluene. After dissolving in 11ml and stirred for 4 days at 80 ℃. The solution was filtered after the resultant solid was slowly added to methanol 500ml, washed, and dried to the desired product poly [(2,6- (4,4-bis (2'-ethylhexyl) -4 H - cyclopenta [def] Phenanthrene))- alt- (5,5- (4 ', 7'-di (cyen-2-yl) -benzimidazole-2'-spirocyclohexane))] 320 mg.

Example  13

Poly [5,5 ''-(4- ( Hexyloxy )-4''-( Hexyloxy ) -2,2 ': 5', 2 ''- Tersaiofen ) - alt -4,7- (Ben Zimidazole -2- Spycyclohexane )]

1) Synthesis of 2,5-bis (trimethylstenyl) thiophene (Formula 13a)

1 ml (11.12 mmol) of thiophene (Formula 9d) was dissolved in 40 ml of tetrahydrofuran, and slowly added 1.7 M t -butyllithium 26 ml (44.5 mmol) at −78 ° C., followed by stirring for 1 hour at room temperature. After cooling to -78 ° C 1M trimethyltin chloride was added slowly and stirred at room temperature for 12 hours. 100 ml of distilled water was added, extracted with ethyl acetate and distilled water, dried over magnesium sulfite and recrystallized with methanol. 1.71 g (38%) of a white solid were obtained.

¹ H NMR (300 MHz, Acetone-d ₆ ) δ 7.37 (s, 2H), 0.36 (s, 18H)

2) Synthesis of 4,7-bis- (3-hexyloxy-thiophen-2-yl) -benzimidazole-2-spirocyclohexane (Formula 13b)

0.5 g (19.20 mmol) of magnesium and catalytic amount of iodine were dissolved in 15 ml of tetrahydrofuran, and 2.6 g (9.60 mmol) of 2-bromo-3- (hexyloxy) thiophene (Formula 8c) was dissolved in 15 ml of tetrahydrofuran. The solution was added slowly and stirred at 50 ° C. for 3 hours. The solution was diluted with 4,7-dibromobenzimidazole-2-spirocyclohexane (1h) and 1,3-bis [(diphenylphosphino) -propane] dichloro nickel (II) 50 mg (0.096 mmol). Was slowly added to a solution dissolved in 20 ml of tetrahydrofuran and stirred at 50 ° C. for 18 hours. 100 ml of distilled water was added, the mixture was extracted with ether and saturated aqueous ammonium chloride solution, dried over magnesium sulfite, and the liquid residue produced by vacuum distillation of the solvent was separated by column chromatography. 270 mg (15%) of purple liquid were obtained.

R _f = 0.57 (SiO ₂ , ethyl acetate: hexane = 1: 10)

¹ H NMR (300 MHz, Acetone-d ₆ ) δ 8.09 (s, 2H), 7.47 (d, 2H, J = 5.7 Hz), 7.07 (d, 2H, J = 5.7 Hz), 4.22 (t, 4H, J = 6.3 Hz), 1.85 (m, 4H), 1.57 (m, 4H), 1.40 (m, 10H), 1.85 (m, 8H), 0.93 (m, 6H)

3) Synthesis of 4,7-bis- (5-bromo-3-hexyloxy-thiophen-2-yl) benzimidazole-2-spirocyclohexane (Formula 13c)

270 mg (0.49 mmol) of the compound of Chemical Formula 13b thus obtained was dissolved in 45 ml of tetrahydrofuran, and 4.83 g (27.13 mmol) of N -bromosuccinimide was added at room temperature, followed by stirring for 12 hours. The product was isolated by column chromatography, extracting with ethyl acetate and saturated aqueous sodium bicarbonate solution, drying with magnesium sulfite and distilling off the solvent in vacuo. 260 mg (76%) of a purple solid were obtained.

R _f = 0.23 (SiO ₂ , Ethyl acetate: hexane = 1:50)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.90 (s, 2H), 6.89 (s, 2H), 4.08 (t, 4H, J = 6.3 Hz), 1.99-1.81 (m, 4H), 1.79 (m, 4H), 1.56-1.49 (m, 8H), 1.47-1.25 (m, 10H), 0.91 (m, 6H)

4) poly [5,5 '- (4- (hexyloxy) -4''- (hexyloxy) -2,2': 5'2 '' - between the emitter-thiophene) - alt -4,7 -(Benzimidazole-2-spirocyclohexane)] (Formula 13d)

Thus obtained 350 mg (0.494 mmol) of the compound of Formula 13c, 200 mg (0.494 mmol) of the compound of Formula 13a, and 17.1 mg (0.0149 mmol) of tetrakis (triphenylphosphine) palladium (0) were added with 4 ml of toluene and N , N -di It was dissolved in 1 ml of methyl formamide and stirred at 100 ° C. for 24 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to give the desired product poly [5,5 ''-(4- (hexyloxy) -4 ''-(hexyloxy) -2, 2 ': 5', 2'- terthiophene) -alt- 4,7- (benzimidazole-2-spirocyclohexane)] 230 mg.

Example  14

Poly [(2 ', 5- (3'- Hexyloxy ) -5 '-(2- Sienil ) Thiophene ) - co -(5 ', 7- (2,2- Dihexyl ) -4- (2'- Sienil )-2 H - Benzimidazole )] s, TOHT - co - BCHT10  (Formula 14e), TOHT - co BCHT30 (Formula 14f), TOHT - co - BCHT50  (Formula 14g), TOHT - co - BCHT70  Formula 14h), Preparation of TOHT-co-BCHT90 (Formula 14i)

1) Synthesis of 2,5-Dibromo-3- (hexyloxy) thiophene (Formula 14a)

1.1 g (5.97 mmol) of 3- (hexyloxy) thiophene (Formula 8b) was dissolved in 20 ml of chloroform and 20 ml of acetic acid, followed by addition of 2.13 g (11.94 mmol) of N -bromosuccinimide at room temperature, followed by stirring for 10 minutes. It was. After adding 50 ml of distilled water, 20 ml of 10% aqueous potassium hydroxide solution was added, extracted with chloroform and distilled water, dried over magnesium sulfite, and the liquid solid residue formed by vacuum distillation of the solvent was separated through column chromatography. 1.3 g (64%) of a colorless liquid were obtained.

R _f = 0.51 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 6.75 (s, 1H), 3.98 (t, 2H, J = 6.60 Hz), 1.75-1.68 (q, 2H, J = 6.60 Hz), 1.34-1.29 (m, 6H), 0.91-0.07 (m, 3H)

2) Synthesis of 4,7-Dibromo-2,2-dihexyl-2,3-dihydro-1 H -benzimidazole (Formula 14c)

3.54 g (13.31 mmol) of 3,6-dibromo-1,2-benzenediamine (Formula 1f) was dissolved in 30 ml of ether and 4 ml of acetic acid, and 3.2 ml (13.32 mmol) of dihexyl ketone (Formula 14b) were added at 50 ° C. Stir for 3 days after addition. 70 ml of distilled water was added, the mixture was extracted with ethyl acetate and distilled water, dried over magnesium sulfate, and the liquid residue produced by vacuum distillation of the solvent was separated through column chromatography. 3.68 g (62%) of a colorless liquid were obtained.

R _f = 0.37 (SiO ₂ , ethyl acetate: hexane = 1:10)

¹ H NMR (300 MHz, Acetone-d6) δ 6.42 (s, 2H), δ 5.39 (s, 2H), 1.70 (m, 6H), 1.6-1.2 (br, 16H), 0.86 (m, 4H)

3) Synthesis of 4,7-Dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d)

3.68 g (8.246 mmol) of the compound of Formula 14c thus obtained was dissolved in 150 ml of methylene chloride, and then 10 g (98.95 mmol) of 85% manganese dioxide (IV) was added at room temperature. After stirring for 1 hour at room temperature, the mixture was filtered through celite, extracted with methylene chloride and distilled water, and dried over magnesium sulfite. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 2.5 g (68%) of a yellow solid were obtained.

R _f = 0.44 (SiO ₂ , ethyl acetate: hexane = 1: 10)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.2 (S, 2H), 2.18 (m, 4H), 1.3-1.0 (br, 12H), 1.0-0.7 (br, 10H)

4) Poly [(2'-5- (3'-hexyloxy) -5 '-(2-cyenyl) thiophene) -co- (5', 7- (2,2-dihexyl)- 4- (2'-cyenyl) -2 H -benzimidazole)] s, TOHT-co-BCHT10 (Formula 14e)

300 ml (0.732 mmol) of the compound of Formula 13a, 200 mg (0.657 mmol) of the compound of Formula 14a, 30 mg (0.073 mmol) of the compound of Formula 14d, and 25 mg (0.0219 mmol) of tetrakis (triphenylphosphine) palladium (0) 4 ml of toluene And N and N -dimethylformamide were dissolved in 1 ml and stirred at 100 ° C. for 40 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene. ) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, to obtain a TOHT-co-BCHT10 130mg.

5) Poly [(2'5- (3'-hexyloxy) -5 '-(2-cyenyl) thiophene) -co- (5', 7- (2,2-dihexyl) -4 synthesis of benzimidazole)] s, TOHT-co- BCHT30 ( formula 14f) - (2 ' between carbonyl) -2 H

300 mg (0.732 mmol) of the compound of Formula 13a, 170 mg (0.511 mmol) of the compound of Formula 14a, 97 mg (0.219 mmol) of the compound of Formula 14d, and 25 mg (0.0219 mmol) of tetrakis (triphenylphosphine) palladium (0) 10 ml of toluene It was dissolved in and stirred at 100 ° C. for 40 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene. ) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, TOHT-co- BCHT30 give the 150mg.

6) Poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene) -co- (5 ', 7- (2,2-dihexyl)- 4- (2'-cyenyl) -2 H -benzimidazole)] s, TOHT-co-BCHT50 (Formula 14g)

300 ml (0.732 mmol) of the compound of Formula 13a, 130 mg (0.366 mmol) of the compound of Formula 14a, 160 mg (0.366 mmol) of the compound of Formula 14d, and 25 mg (0.0073 mmol) of tetrakis (triphenylphosphine) palladium (0) 4 ml of toluene And N and N -dimethylformamide were dissolved in 1 ml and stirred at 100 ° C. for 40 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene. ) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, to obtain a TOHT-co-BCHT50 200mg.

7) Poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene) -co- (5 ', 7- (2,2-dihexyl)- 4- (2'-cyenyl) -2 H -benzimidazole)] s, TOHT-co-BCHT70 (Formula 14h)

330 mg (0.810 mmol) of compound of formula 13a, 83 mg (0.243 mmol) of compound of formula 14a, 250 mg (0.567 mmol) of compound of formula 14d, and 25 mg (0.0219 mmol) of tetrakis (triphenylphosphine) palladium (0) 4 ml of toluene And N and N -dimethylformamide were dissolved in 1 ml and stirred at 100 ° C. for 40 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene. ) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, to obtain a TOHT-co-BCHT70 200mg.

8) Poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene) -co- (5'-7- (2,2-dihexyl)- 4- (2'-cyenyl) -2 H -benzimidazole)] s, synthesis of TOHT-co-BCHT90 (Formula 14i)

300 ml (0.732 mmol) of the compound of Formula 13a, 25 mg (0.073 mmol) of the compound of Formula 14a, 290 mg (0.659 mmol) of the compound of Formula 14d and 25 mg (0.0219 mmol) of tetrakis (triphenylphosphine) palladium (0) 4 ml of toluene And N and N -dimethylformamide were dissolved in 1 ml and stirred at 100 ° C. for 40 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [(2 ', 5- (3'-hexyloxy) -5'-(2-cyenyl) thiophene. ) -co- (5'-7- (2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, to obtain a TOHT-co-BCHT90 180mg.

Example  15

Poly [2,6- (4,4- Dimethyl -4 H Cyclopenta [2,1-b: 3,4- b ' ] Daissai pen ) - alt -4,7- (Ben Zumi Dozol-2- Spycyclohexane )]

1) Synthesis of 4,4-dimethyl- 4H -cyclopenta [2,1-b: 3,4-b '] diocyphene (Formula 15a)

In: [3,4-b '2,1- b] thiophene between the die (Formula 2e) 2.25g (12.621mmol) and triethyl benzyl ammonium chloride 57mg dimethyl sulfoxide 30ml (0.252mmol) cyclopenta - 4 H After dissolving, the mixture was stirred at 60 ° C. for 2 hours, and then 3.15 ml (50.485 mmol) of iodomethane was added thereto, stirred at room temperature for 5 minutes, and then 1.84 ml (31.553 mmol) of 50% sodium hydroxide was added thereto, followed by stirring at room temperature for 12 hours. The product was isolated by column chromatography, and extracted with methylene chloride and distilled water, dried over magnesium sulfate, and distilled off the solvent under vacuum distillation. 1.84 g (71%) of a yellow solid were obtained.

R _f = 0.43 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.16 (d, 2H, J = 5.1 Hz), 7.00 (d, 2H, J = 5.1 Hz), 1.45 (s, 6H)

2) 4,4-dimethyl-2,6-bis (4 ′, 4 ′, 5 ′, 5′-tetramethyl-1 ′, 3 ′, 2′-dioxaborolane-2-yl) -4 H Synthesis of -cyclopenta- [2,1-b: 3,4-b '] diocyopene (Formula 15b)

1 g (4.846 mmol) of the compound of Chemical Formula 15a and 2.18 ml (14.539 mmol) of tetramethylethylenediamine were dissolved in 20 ml of tetrahydrofuran, and 9.08 ml (14.539 mmol) of 1.6 M n -butyllithium was slowly dried at -78 ° C. After the addition, the mixture was stirred for 30 minutes, stirred at room temperature for 1 hour, cooled to -78 ° C, and then 4ml (19.384mmol) of isopropoxy-4,4,5,5-tetramethyl [1,3,2] dioxaborolane. Was added slowly and stirred for 30 minutes and then stirred at room temperature for 12 hours. After adding 1 ml of distilled water, the mixture was extracted with ethyl acetate and saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate, and the solid residue produced by vacuum distillation of the solvent was separated by column chromatography. 1.15 g (52%) of a yellow solid was obtained.

R _f = 0.21 (SiO ₂ , ethyl acetate: hexane = 1: 10)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.5 (s, 2H), 1.43 (s, 6H), 1.35 (s, 24H)

3) Poly [2,6- (4,4-dimethyl- 4H -cyclopenta [2,1-b: 3,4-b '] diithiophene) -alt- 4,7- (benzimidazole -2- Spirocyclohexane)] (Formula 15c)

Thus obtained 350 mg (0.764 mmol) of the compound of Formula 15b, 263 mg (0.764 mmol) of the compound of Formula 1h, 3.8 ml of a 2M potassium carbonate aqueous solution and 26 mg (0.023 mmol) of tetrakis (triphenylphosphine) palladium (0) 5 ml of toluene It was dissolved in and stirred at 80 ° C for 4 days. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [2,6- (4,4-dimethyl-4 H -cyclopenta [2,1-b: 3,4 72 mg of [b '] diocyphene) -alt- 4,7- (benzimidazole-2-spirocyclohexane)] were obtained.

Example  16

Poly [2,6- (4,4- Dimethyl -4 H Cyclopenta [2,1-b: 3,4- b ' ] Daissai pen ) - alt -4,7- (2,2-dihexyl-2 H - Benzimidazole )]

1) Poly [2,6- (4,4-dimethyl- 4H -cyclopenta [2,1-b: 3,4-b '] diocyphene) -alt- 4,7- (2,2 -Dihexyl- 2H -benzimidazole)] (Formula 16a)

4,4-dimethyl-2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lorraine-2-yl) -4 H - cyclopenten 248 mg (0.540 mmol) of penta- [2,1-b: 3,4-b '] diocyphene (Formula 15b) and 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole ( Formula 14d) 240 mg (0.540 mmol), 2.7 ml of 2M potassium carbonate solution, and 18.7 mg (0.016 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in 5 ml of toluene, followed by stirring at 80 ° C. for 4 days. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [2,6- (4,4-dimethyl-4 H -cyclopenta [2,1-b: 3,4 -b '] dicyiophen) -alt -4,7- (2,2-dihexyl- 2H -benzimidazole)] 72 mg.

Example  17

Poly [2,5- ( Thiophene ) - alt -4,7- (2,2- Dihexyl -2 H - Benzimidazole )]

1) Synthesis of Poly [2,5- (Ciophene) -alt- 4,7- (2,2-dihexyl- 2H -benzimidazole)] (Formula 17a)

2,5-bis (trimethylstenyl) thiophene (Formula 13a) 277 mg (0.675 mmol) and 4,7-dibromo-2,2-dihexyl-2 H -benzimidazole (Formula 14d) 300 mg (0.675) mmol) and 23 mg (0.0203 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in 5 ml of toluene and stirred at 120 ° C. for 36 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [2,5- (thiophene) -alt -4,7- (2,2-dihexyl- 2H -benz Imidazole)] to 40 mg.

Example  18

Poly [5,5 '-(2,2'- Baissaifen ) - alt -4,7- (2,2- Dihexyl -2 H - Benzimidazole )]

1) Synthesis of 5,5'-bis (trimethylstenyl) -2,2'-bithiophene (Formula 18b)

1 g (6.014 mmol) of 2,2'-bithiophene (Formula 18a) and 18 ml (18.044 mmol) of tetramethylethylenediamine were dissolved in 20 ml of tetrahydrofuran, and 11.28 ml (18.044) of 1.6 M n -butyllithium at -78 ° C. mmol) was added slowly, followed by stirring for 1 hour, followed by stirring at room temperature for 3 hours. After cooling to -78 ° C 1M trimethyltin chloride was added slowly and stirred at room temperature for 12 hours. 100 ml of distilled water was added, extracted with ethyl acetate and distilled water, dried over magnesium sulfite and recrystallized with methanol. 2.2 g (80%) of a white solid were obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.29 (d, 2H, J = 3.3 Hz), 7.10 (d, 2H, J = 3.3 Hz), 0.39 (s, 18H)

2) Synthesis of Poly [5,5 '-(2,2'-Biothiophene) -alt- 4,7- (2,2-dihexyl- 2H -benzimidazole)] (Formula 18c)

Thus obtained compound of formula 18b 300mg (0.658mmol) and 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) 292mg (0.658mmol) and tetrakis (triphenylphosphine ) 22.8 mg (0.0197 mmol) of palladium (0) was dissolved in 10 ml of toluene and stirred at 120 ° C. for 24 hours. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [5,5 '-(2,2'-bithiophene) -alt -4,7- (2,2- Dihexyl-2 H -benzimidazole)] 160 mg.

Example  19

Poly [5,5 ''-(2,2'5 ', 2' '- Tersaiofen ) - alt -4,7- (2,2- Dihexyl -2 H - Benzimida Sol)]

1) Synthesis of 2- (tributylstenyl) thiophene (Formula 19a)

2.85ml (35.655mmol) of thiophene (Formula 9d) was dissolved in 80ml of tetrahydrofuran, and slowly added 1.6M n -butyllithium 24.51ml (39.22mmol) at -78 ° C, followed by stirring for 2 hours, followed by tributyltin chloride. Slowly added and stirred for 2 hours. 50 ml of saturated aqueous sodium bicarbonate solution was added, extracted with ether and distilled water, dried over magnesium sulfite and filtered with neutral alumina. 13 g (97%) of a colorless liquid were obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ7.68 (dd, 1H, J = 0.9, 4.5 Hz), 7.29 (m, 1H), 7.23 (dd, 1H, J = 0.6, 3.3 Hz), 1.60 (m , 6H, J = 2.4 Hz), 1.36 (m, 6H), 1.16 (m, 6H), 0.95 (t, 9H, J = 7.5 Hz)

Synthesis of benzimidazole (Formula 19b) - 2) 2,2- dimethyl-hexyl-4,7-di (carbonyl) -2 H between 2

Thus obtained compound 4g (10.715mmol) and 4,7-dibromo-2,2-dihexyl-2 H -benzimidazole (Formula 14d) 1.19g (2.679mmol) and bis (triphenylphosphine) ) Dichloro palladium 38 mg (0.054 mmol) was dissolved in 40 ml of tetrahydrofuran and stirred at 80 ° C. for 24 hours. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 0.32 g (27%) of a red solid was obtained.

R _f = 0.72 (SiO ₂ , methylene chloride: hexane = 1: 2)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.02 (dd, 2H, J = 1.2, 3.6 Hz), 7.37 (dd, 2H, J = 1.2, 5.1 Hz), 7.30 (s, 2H), 7.14 (dd , 2H, J = 3.9, 5.1 Hz), 2.17 (m, 4H), 1.36 (m, 4H), 1.19 (m, 12H), 0.92 (m, 2H), 0.82 (m, 4H)

3) Synthesis of 4,7-bis (5-bromo-2-cyenyl) -2,2-dihexyl- 2H -benzimidazole (Formula 19c)

The 320 mg (0.710 mmol) of the compound of Chemical Formula 19b was dissolved in 50 ml of tetrahydrofuran, and 0.252 g (1.420 mmol) of N -bromosuccinimide was slowly added thereto at 0 ° C., followed by stirring for 12 hours. After adding 100 ml of distilled water, the solvent was distilled in vacuo, extracted with ethyl acetate and distilled water, dried over magnesium sulfate, and the solid residue produced by vacuum distillation of the solvent was separated through column chromatography. 400 mg (93%) of a red solid were obtained.

R _f = 0.68 (SiO ₂ , methylene chloride: hexane = 1: 2)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.26 (d, 2H, J = 3.9 Hz), 7.21 (s, 2H), 7.07 (d, 2H, J = 3.9 Hz), 2.14 (m, 4H), 1.25 (m, 12H), 1.15-1.00 (br, 4H) 0.9-0.8 (br, 6H)

4) Poly [5,5 ''-(2,2 ': 5', 2 ''-terthiophene) -alt- 4,7- (2,2-dihexyl- 2H -benzimidazole)] Synthesis of Formula 19d

Thus obtained compound of formula 19c 300mg (0.493mmol) and 2,5-bis (trimethylstenyl) thiophene (Formula 13a) 202mg (0.493mmol) and tetrakis (triphenylphosphine) palladium (0) 17.1mg (0.0148 mmol) was dissolved in 7 ml of toluene and stirred at 120 ° C. for 24 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to give the desired product poly [5,5 ''-(2,2 ': 5', 2 ''-teriophene) -alt- 4 , 7- (2,2-dihexyl- 2H -benzimidazole)] (Formula 19d) was obtained 179 mg.

Example  20

Poly [2,7- (9- (2- Ethylhexyl ) -9 H - Carbazole ) - alt -5,5- (4 ', 7'- die (Cyen-2-yl) -2,2-da this Hexyl-2 H - Benzimidazole )]

1) Synthesis of 2,7-Dibromo-9- (2-ethylhexyl) -9 H -carbazole (Formula 20a)

0.236 mg (5.91 mmol) of sodium hydride are dissolved in 11 ml of N , N -dimethylformamide, and 1.6 g (4.92 mmol) of 2,7-dibromo-9 H -carbazole (Formula 9j) is added N , N at 0 ° C. It was dissolved in 11 ml of dimethylformamide, and slowly added thereto. The mixture was stirred at 0 ° C. for 30 minutes, and then 1.38 ml (7.38 mmol) of 2-ethylhexyl bromide was added thereto, followed by stirring at room temperature for 24 hours. After cooling to 0 ° C., 10 ml of distilled water was added, followed by vacuum distillation. The remaining residue was extracted with ethyl acetate and distilled water, and dried over magnesium sulfate. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 1.84 g (85%) of a white solid were obtained.

R _f = 0.5 (SiO ₂ , ethyl acetate: hexane = 1: 8)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.88 (d, 2H), 7.49 (d, 2H), 7.35 (dd, 2H), 4.05 (m, 2H), 2.00 (m, 1H), 1.35 (m, 8H), 0.91 (m, 6H)

2) 2,7-bis (4,4,5,5-tetramethyl-1,3,2 dioxane Sabo Lauren-2-yl) - Synthesis of (2-ethylhexyl) carbazole (Formula 20b) - N

Thus obtained 1.5 g (3.43 mmol) of the compound of formula 20a was dissolved in 22 ml of tetrahydrofuran, and 4.50 ml (7.20 mmol) of 1.6M n -butyllithium was slowly added at -78 ° C, and stirred for 1 hour, followed by isopropoxy-4. 1.75ml (8.58mmol) of 4,5,5-tetramethyl [1,3,2] dioxaborolane was added thereto, followed by stirring for 1 hour and then stirred at room temperature for 12 hours. After adding 10 ml of distilled water, the mixture was extracted with ether and distilled water, dried over magnesium sulfite, and the solid residue produced by vacuum distillation of the solvent was separated through column chromatography. 1.08 g (59%) of a white solid were obtained.

R _f = 0.2 (SiO ₂ , Ethyl acetate: hexane = 1:10)

¹ H NMR (300 MHz, CDCl ₃ ) δ8.11 (d, 2H), 7.88 (s, 2H), 7.66 (d, 2H), 4.26 (m, 2H), 2.12 (m, 1H), 1.39 (m , 32H), 0.90 (m, 6H)

3) Synthesis of (Formula 20c)

Thus obtained 198 mg (0.373 mmol) of the compound of Formula 20b, 227 mg (0.373 mmol) of the compound of Formula 19c, 2 ml of 2M aqueous potassium carbonate solution, and 12.9 mg (0.011 mmol) of tetrakis (triphenylphosphine) palladium (0) were obtained. After dissolving in 10ml and stirred for 4 days at 80 ℃. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly [2,7- (9- (2-ethylhexyl) -9 H -carbazole) -alt -5,5- (4 ', 7'-di (cyen-2-yl) -2,2-dihexyl- 2H -benzimidazole)] 100 mg.

Example  21

Poly [(5 ', 6- (4,4- Dihexyl ) -2- (2'- Sienil )-4 H Cyclopenta [2,1-b: 3,4- b ' Daisai pen) co -(5 ', 7- (2,2- Dihexyl ) -4- (2'- Sienil )-2 H - Benzimidazole )] s, PCPDTT-co-BCHT10 (Formula 21c), PCPDTT - co - BCHT30  (Formula 21d), PCPDTT - co - BCHT50  (Formula 21e), PCPDTT - co - BCHT70  (Formula 21f), PCPDTT - co - BCHT90  Of Formula 21g My article

1) Synthesis of 4,4-Dihexyl- 4H -cyclopenta [2,1-b: 3,4-b '] diocyphene (Formula 21a)

In: [3,4-b '2,1- b] thiophene between the die (Formula 2e) 1.5g (8.414mmol) and triethyl benzyl ammonium chloride 38mg dimethyl sulfoxide 30ml (0.168mmol) cyclopenta - 4 H After dissolving, the mixture was stirred at 60 ° C. for 2 hours, and then 2.3 ml (21.036 mmol) of 1-bromohexane was added, 1.2 ml (21.036 mmol) of 50% sodium hydroxide was added thereto, and the mixture was stirred at 60 ° C. for 12 hours. The product was isolated by column chromatography, and extracted with methylene chloride and distilled water, dried over magnesium sulfate, and distilled off the solvent under vacuum distillation. 1.8 g (62%) of a colorless liquid were obtained.

R _f = 0.46 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.15 (dd, 2H, J = 0.9, 4.8 Hz), 6.93 (dd, 2H, J = 0.9, 4.8 Hz), 1.78 (m, 4H), 1.13 (m, 12H), 0.94 (m, 4H), 0.81 (m, 6H)

2) Synthesis of 2,6-dibromo-4,4-dihexyl- 4H -cyclopenta [2,1-b: 3,4-b '] dithiophene (Formula 21b)

2.117 g (6.108 mmol) of the compound of Formula 21a thus obtained was dissolved in 200 ml of tetrahydrofuran, and then 2.174 g (12.216 mmol) of N -bromosuccinimide was added little by little at 0 ° C., followed by stirring at room temperature for 12 hours. After adding 100 ml of distilled water, the solvent was distilled under vacuum, extracted with ether and distilled water, dried over magnesium sulfite, and the liquid residue produced by vacuum distillation of the solvent was separated through column chromatography. 2.6 g (85%) of yellow liquid were obtained.

R _f = 0.73 (SiO ₂ , hexane 100%)

¹ H NMR (300 MHz, CDCl ₃ ) δ 6.92 (s, 2H), 1.72 (m, 4H), 1.3-1.0 (br, 12H), 0.82 (m, 10H)

3) Poly [(5 ', 6- (4,4-dimethyl-hexyl) -2- (2 ' between carbonyl) -4 H - cyclopenta [2,1-b: 3,4- b' ] di between thiophene) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, PCPDTT-co- BCHT10 ( formula 21c ) Synthesis

Thus obtained compound of formula 21b 334mg (0.659mmol) and 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) 32.5mg (0.0732mmol) and 2,5-bis ( Trimethylstenyl) thiophene (Formula 13a) 300 mg (0.732 mmol) and tetrakis (triphenylphosphine) palladium (0) 25.4 mg (0.022 mmol) were dissolved in 7 ml of toluene and stirred at 120 ° C. for 36 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [(5'-6- (4,4-dihexyl) -2- (2'-cyenyl) -4 H -cyclopenta [2,1-b: 3,4-b '] diocyopene) -co- (5'-7- (2,2-dihexyl) -4- (2'-cyenyl) -2 H - benzimidazole)] s, to obtain a PCPDTT-co-BCHT10 200mg.

4) poly [(5'-6- (4,4-dimethyl-hexyl) -2- (2 ' between carbonyl) -4 H - cyclopenta [2,1-b: 3,4-di b'- Thiophene) -co- (5'-7- (2,2-dihexyl) -4- (2'-cyenyl) -2 H -benzimidazole)] s, PCPDTT-co-BCHT30 (Formula 21d) ) Synthesis

Thus obtained compound of formula 21b 253 mg (0.501 mmol) and 4,7-dibromo-2,2-dihexyl-2 H -benzimidazole (Formula 14d) 95.3 mg (0.215 mmol) and 2,5-bis ( 293 mg (0.715 mmol) of trimethylstenyl) thiophene (Formula 13a) and 24.8 mg (0.0215 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in 8 ml of toluene and stirred at 120 ° C. for 18 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [(5'-6- (4,4-dihexyl) -2- (2'-cyenyl) -4 H -cyclopenta [2,1-b: 3,4-b'-dithiophene) -co- (5'-7- (2,2-dihexyl) -4- (2'-cyenyl) -2 H - benzimidazole)] s, to obtain a PCPDTT-co-BCHT30 180mg.

5) Poly [(5'-6- (4,4-dimethyl-hexyl) -2- (2 ' between carbonyl) -4 H - cyclopenta [2,1-b: 3,4-di b'- between thiophene) -co- (5'-7- (2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, PCPDTT-co- BCHT50 ( formula 21e ) Synthesis

185 mg (0.366 mmol) of the compound of formula 21b and 163 mg (0.366 mmol) of 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) and 2,5-bis (tri) Methylstenyl) thiophene (Formula 13a) 300 mg (0.732 mmol) and tetrakis (triphenylphosphine) palladium (0) 25 mg (0.022 mmol) were dissolved in 8 ml of toluene and stirred at 120 ° C. for 20 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [(5'-6- (4,4-dihexyl) -2- (2'-cyenyl) -4 H -cyclopenta [2,1-b: 3,4-b'-diocyopene) -co- (5'-7- (2,2-dihexyl) -4- (2'-cyenyl) -2 H - benzimidazole)] s, to obtain a PCPDTT-co-BCHT50 170mg.

6) Poly [(5'-6- (4,4-dimethyl-hexyl) -2- (2 ' between carbonyl) -4 H - cyclopenta [2,1-b: 3,4-b '] di between thiophene) -co- (5 ', 7- ( 2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, PCPDTT-co- BCHT70 ( 21f formula ) Synthesis

Thus obtained compound 126mg (0.251mmol) of formula 21b and 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) 260mg (0.585mmol) and 2,5-bis (tri Methylstenyl) thiophene (Formula 13a) 342 mg (0.835 mmol) and tetrakis (triphenylphosphine) palladium (0) 28.9 mg (0.025 mmol) were dissolved in 8 ml of toluene and stirred at 120 ° C. for 18 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [(5'-6- (4,4-dihexyl) -2- (2'-cyenyl) -4 H -cyclopenta [2,1-b: 3,4-b '] diocyopene) -co- (5', 7- (2,2-dihexyl) -4- (2'-cyenyl) -2 H - benzimidazole)] s, to obtain a PCPDTT-co-BCHT70 100mg.

7) poly [(5'-6- (4,4-dimethyl-hexyl) -2- (2 ' between carbonyl) -4 H - cyclopenta [2,1-b: 3,4-b '] - Using the method of the die between -co- (5'-7- (2,2- dimethyl-hexyl) -4- (2 ' between carbonyl) -2 H - benzimidazole)] s, PCPDTT-co- BCHT90 ( 21g formula ) Synthesis

34.2 mg (0.0678 mmol) of the compound of formula 21b and 271 mg (0.610 mmol) of 4,7-dibromo-2,2-dihexyl- 2H -benzimidazole (Formula 14d) thus obtained were obtained. 278 mg (0.678 mmol) of trimethylstenyl) thiophene (Formula 13a) and 23.5 mg (0.0203 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in 8 ml of toluene and 2 ml of N , N -dimethylformamide. After stirring at 120 ° C for 18 hours. The solution was slowly added to 500 ml of methanol and the resulting solid was filtered, washed and dried to afford the desired product poly [(5'-6- (4,4-dihexyl) -2- (2'-cyenyl) -4 H -cyclopenta [2,1-b: 3,4-b'diiocene) -co- (5'-7- (2,2-dihexyl) -4- (2'-cyenyl)- 2 H -benzimidazole)] s, PCPDTT-co-BCHT90 50 mg was obtained.

The molecular weight was measured using GPC, and the measured molecular weight was 6,000-31,000, the number average molecular weight was 10,000-158,000, and the dispersity was 1.2-5.1. These polymers showed maximum absorption at 500-850 nm.

The polymers prepared and synthesized in Examples 1 to 21 had excellent solubility in organic solvents and were completely dissolved in general organic solvents. The benzimidazole-based copolymer according to the present invention is well dissolved in a general organic solvent, and thus room temperature spin coating can be performed. I can make it.

1 shows, for example, a cross-sectional view of an organic polymer thin film solar cell device using these polymers as a solar absorption layer. Referring to FIG. 1, a translucent electrode is formed on a substrate, a hole transport layer and a solar absorbing organic semiconductor layer are formed on the translucent electrode, and a metal electrode is formed on the organic semiconductor layer. In the embodiment of the present invention, a thin film solar cell device was manufactured using ITO and aluminum (Al) coated on glass as a cathode and an anode, respectively.

Example  22

Fabrication of Organic Polymer Thin Film Solar Cell Devices

A semitransparent electrode 2 of indium tin oxide (ITO) is formed on the glass substrate 1, and a 50 nm thick conductive polymer (Baytron P, HC Starck) is formed on the semitransparent electrode 2. A hole transporting layer 3 was formed.

The polymer prepared in Examples 1 and 21 and PCBM ([6,6] -phenyl-C61-butyric acid methylester) were mixed 1: 3 (w / w) on the hole transport layer 3 by spin coating. A device for measuring photoelectric efficiency was formed by forming a 100 nm-thick photovoltaic organic semiconductor layer 4 and forming an aluminum (Al) metal electrode 5 using aluminum on the organic semiconductor layer 4. .

Evaluation results

FIG. 2 shows absorption spectra of organic polymer thin film solar cell devices fabricated using the polymers prepared in Examples 1 to 5. FIG. 3 shows absorption spectra of organic polymer thin film solar cell devices fabricated using the polymers prepared in Examples 6 to 8. FIG. FIG. 4 shows absorption spectra of organic polymer thin film solar cell devices fabricated using the polymers prepared in Examples 9 to 12. FIG. 5 shows absorption spectra of organic polymer thin film solar cell devices fabricated using the polymers prepared in Examples 13 to 14. FIG. FIG. 6 shows absorption spectra of organic polymer thin film solar cell devices fabricated using the polymers prepared in Examples 15 to 20. FIG. FIG. 7 shows an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 21. FIG.

2 to 7, it is possible to identify a wide range of light absorption bands in the visible light region. Therefore, it can be seen that the organic polymer thin film solar cell device can be manufactured using the polymer material according to the present invention.

FIG. 8 illustrates a device manufactured from the polymer prepared in Example 2 by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 8 was found to be 0.18% at 100 mW / cm ² light. FIG. 9 illustrates a device manufactured from the polymer prepared in Example 9 by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 9 was found to be 0.91% at 100 mW / cm ² light. FIG. 10 illustrates a device manufactured from the polymer prepared in Example 11 by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 10 was found to be 1.01% at 100 mW / cm ² light.

8 to 10, it can be seen that the photovoltaic properties of the organic thin film solar cell device using the polymer material according to the present invention are very excellent.

11 and 12 are graphs showing voltages and current densities of organic light emitting diodes manufactured by using the polymer prepared in Example 9. FIG. 11 and 12 show typical semiconductor characteristics in which current density increases with increasing voltage. Therefore, it can be seen that the polymer material of the present invention can be used as an organic semiconductor material.

1 is a cross-sectional view of an organic polymer thin film solar cell device using a polymer according to the present invention.

FIG. 2 is a graph illustrating absorption spectra of organic polymer thin film solar cell devices using the polymers of Examples 1 to 5. FIG.

3 is a graph illustrating absorption spectra of organic polymer thin film solar cell devices using the polymers of Examples 6 to 8. FIG.

4 is a graph illustrating absorption spectra of organic polymer thin film solar cell devices using the polymers of Examples 9 to 12. FIG.

FIG. 5 is a graph illustrating absorption spectra of organic polymer thin film solar cell devices using the polymers of Examples 13 to 14. FIG.

6 is a graph illustrating absorption spectra of organic polymer thin film solar cell devices using the polymers of Examples 15 to 20. FIG.

FIG. 7 is a graph illustrating an absorption spectrum of an organic polymer thin film solar cell device using the polymer of Example 21. FIG.

8 is a graph illustrating photoelectric efficiency measurement of an organic polymer thin film solar cell device using the polymer of Example 2. FIG.

9 is a graph illustrating photoelectric efficiency measurement of an organic polymer thin film solar cell device using the polymer of Example 9. FIG.

10 is a graph illustrating photoelectric efficiency measurement of an organic polymer thin film solar cell device using the polymer of Example 11. FIG.

11 and 12 are graphs illustrating voltage and current measurements of the organic thin film transistor using the polymer of Example 9. FIG.

Description of the Related Art [0002]

1: substrate

2: translucent electrode

3: hole transport layer

4: solar absorption organic semiconductor layer

5: metal electrode

Claims (16)

Benzimidazole-based copolymer represented by the formula (1): <Formula 1>

In the above formula, D is an electron donor represented by Formula 2, A is a benzimidazole derivative selected from Formulas 6 to 9, n is an integer of 10 to 150, <Formula 2>

, <Formula 6>

, <Formula 7>

, <Formula 8>

, <Formula 9>

Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom, a ketone group, a hydroxyl group, a C _3-20 linear or branched alkyl group, a C _3-20 linear or branched alkoxy Group, C _2-20 linear alkoxyalkyl group, C _4-20 branched alkoxyalkyl group, C _7-20 linear alkoxyphenyl group. delete Benzimidazole-based copolymer represented by the formula (1): <Formula 1>

In the above formula, D is an electron donor represented by Formula 3, A is a benzimidazole derivative selected from Formulas 6 to 9, n is an integer of 10 to 150, <Formula 3>

, <Formula 6>

, <Formula 7>

, <Formula 8>

, <Formula 9>

Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom, a ketone group, a hydroxyl group, a C _3-20 linear or branched alkyl group, a C _3-20 linear or branched alkoxy Group, C _2-20 linear alkoxyalkyl group, C _4-20 branched alkoxyalkyl group, C _7-20 linear alkoxyphenyl group. Benzimidazole-based copolymer represented by the formula (1): <Formula 1>

In the above formula, D is an electron donor represented by Formula 4, A is a benzimidazole derivative selected from Formulas 6 to 9, n is an integer of 10 to 150, <Formula 4>

, <Formula 6>

, <Formula 7>

, <Formula 8>

, <Formula 9>

Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom, a ketone group, a hydroxyl group, a C _3-20 linear or branched alkyl group, a C _3-20 linear or branched alkoxy Group, C _2-20 linear alkoxyalkyl group, C _4-20 branched alkoxyalkyl group, C _7-20 linear alkoxyphenyl group. Benzimidazole-based copolymer represented by the formula (1): <Formula 1>

In the above formula, D is an electron donor represented by Formula 5, A is a benzimidazole derivative selected from Formulas 6 to 9, n is an integer of 10 to 150, <Formula 5>

, <Formula 6>

, <Formula 7>

, <Formula 8>

, <Formula 9>

Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom, a ketone group, a hydroxyl group, a C _3-20 linear or branched alkyl group, a C _3-20 linear or branched alkoxy Group, C _2-20 linear alkoxyalkyl group, C _4-20 branched alkoxyalkyl group, C _7-20 linear alkoxyphenyl group. delete delete delete delete The benzimidazole copolymer according to any one of claims 1 and 3 to 5, wherein the compound represented by Chemical Formula 1 is one selected from the group represented by the following chemical formulas: <Formula 10>

, <Formula 11>

, <Formula 12>

, <Formula 13>

, <Formula 14>

, &Lt; Formula 15 >

, <Formula 16>

, <Formula 17>

, &Lt; Formula 18 >

, <Formula 19>

, <Formula 20>

, <Formula 21>

, <Formula 22>

, <Formula 24>

, <Formula 25>

, <Formula 26>

, <Formula 27>

, <Formula 28>

, And <Formula 29>

In the above formulas, n is an integer of 10 to 150. The benzimidazole copolymer according to any one of claims 1 and 3 to 5, wherein the compound represented by Chemical Formula 1 is one of the following Chemical Formulas: <Formula 23>

or <Formula 30>

Wherein m and n are integers from 10 to 150. The benzimidazole copolymer according to any one of claims 1 to 3, wherein the number average molecular weight is 6,000-31,000 and the mass average molecular weight is 10,000-158,000. An organic polymer thin film solar cell comprising the benzimidazole copolymer according to any one of claims 1 and 3 to 5 as a solar absorbing material. The organic polymer thin film solar cell of claim 13, wherein the solar light absorbing material is thinned by using a spin coating method. An organic thin film transistor comprising the benzimidazole copolymer according to any one of claims 1 and 3 to 5 as an organic semiconductor material. An organic electroluminescent device comprising the benzimidazole copolymer according to any one of claims 1 and 3 to 5 as a light emitting material.

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