KR20100026373A - Copolymers with 4h-cyclopenta[def]phenanthrene (cpp) back-bone and organic polymer thin film solar cells comprising the same - Google Patents

Copolymers with 4h-cyclopenta[def]phenanthrene (cpp) back-bone and organic polymer thin film solar cells comprising the same Download PDF

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KR20100026373A
KR20100026373A KR1020080085351A KR20080085351A KR20100026373A KR 20100026373 A KR20100026373 A KR 20100026373A KR 1020080085351 A KR1020080085351 A KR 1020080085351A KR 20080085351 A KR20080085351 A KR 20080085351A KR 20100026373 A KR20100026373 A KR 20100026373A
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서홍석
이광희
진영읍
김진우
김선희
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Abstract

PURPOSE: A copolymer with 4H-cyclopenta[def]phenanthrene(CPP) back-bone is provided to ensure broad sunlight absorption band, excellent electroconductivity and photoelectric power, and to be useful for an organic polymer solar cell, organic thin film transistor, and organic electroluminescent device. CONSTITUTION: A copolymer has a 4H-cyclopenta[def]phenanthrene(CPP) back-bone represented by chemical formula 1. In chemical formula 1, A is an electron acceptor, D is a 4H-cyclopenta[def]phenanthrene derivative, and n is 10-150. The D is a compound represented by chemical formulas 2 or 3. In chemical formulas 2 and 3, R1 and R2 are independently C1-20 linear or branched alkyl group. The A is a compound represented by chemical formula 4.

Description

4Ｈ―사이클로펜타［ｄｅｆ］페난트렌의 골격을 갖는 공중합체 및 이를 포함하는 유기 고분자 박막 태양 전지 소자{Copolymers with 4H-cyclopenta[def]phenanthrene (CPP) back-bone and organic polymer thin film solar cells comprising the same}Copolymers with 4H-cyclopenta [def] phenanthrene (CPP) back-bone and organic polymer thin film solar cells comprising the copolymer having a skeleton of 4H-cyclopenta phenanthrene same}

본 발명은 4H-사이클로펜타[def]페난트렌 골격을 가진 공중합체 및 이를 포함하는 소자에 관한 것으로, 보다 상세하게는 좁은 밴드 갭을 갖는 4H-사이클로펜타[def]페난트렌 유도체 골격을 가지는 교대 공중합체 및 이를 이용한 유기 고분자 박막 태양 전지 소자에 관한 것이다.The present invention relates to a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton and a device comprising the same, and more particularly, to a 4 H -cyclopenta [ def ] phenanthrene derivative skeleton having a narrow band gap. The present invention relates to an alternating copolymer and an organic polymer thin film solar cell device using the same.

1992년 UCSB의 Heeger가 유기 고분자를 이용한 태양전지 가능성을 최초로 보여준 것을 효시로 현재까지 이에 대하여 많이 연구되고 있다. 이는 유기고분자와 C60를 이종접합 (Bulk Heterojunction)으로 만든 박막소자이며, 유기 고분자가 태양빛을 받은 후 발생한 전자를 전자친화성이 아주 높은 C60가 그 전자를 끌어당겨 이를 전기로 바꾸는 원리이다. 그리하여 현재 유기 고분자를 이용한 유기 고분자 박막 태양전지의 최고 효율은 6.5%에 달하고 있다 (Science, 2007, 307, 222-225). 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 sunlight has a principle of C 60, which has high electron affinity, attracts the electron and converts it into electricity. . Thus, the highest efficiency of the organic polymer thin film solar cell using the organic polymer is 6.5% ( Science , 2007 , 307 , 222-225).

그러나, 현재 실리콘을 이용한 태양전지의 최대효율은 39%로써 유기 고분자 태양전지에 비해 아주 높다. 그리하여 더 높은 효율을 갖는 유기 고분자 태양전지에 대한 개발이 요구되는 현실이다.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.

따라서, 본 발명은 더 넓은 태양광 흡수대역을 가지면서 유기용매에 녹여 상온에서 스핀코팅 공정이 가능한 신규한 공중합체를 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a novel copolymer capable of spin coating at room temperature by dissolving in an organic solvent while having a wider solar absorption band.

또한, 본 발명의 목적은 상기 유기 고분자를 포함하는 유기 고분자 박막 태양전지 소자를 제공하는 것이다.It is also an object of the present invention to provide an organic polymer thin film solar cell device comprising the organic polymer.

또한 본 발명의 다른 목적은 상기 유기 고분자를 유기 반도체 물질로서 포함하는 유기 박막 트랜지스터를 제공한다. Another object of the present invention is to provide an organic thin film transistor including the organic polymer as an organic semiconductor material.

또한 본 발명의 다른 목적은 상기 유기 고분자를 발광 물질로서 포함하는 유기 발광 소자를 제공한다.Another object of the present invention to provide an organic light emitting device comprising the organic polymer as a light emitting material.

상기의 목적을 달성하기 위하여, 본 발명은In order to achieve the above object, the present invention

하기 화학식 1로 표시되는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 제공한다:It provides a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton represented by the following formula (1):

<화학식 1><Formula 1>

Figure 112008061868269-PAT00002
Figure 112008061868269-PAT00002

상기 식에서, A는 전자 수용체이고, D는 4H-사이클로펜타[def]페난트렌 유도체이고, 반복단위 n은 10 내지 150의 정수이다.Wherein A is an electron acceptor, D is a 4H -cyclopenta [ def ] phenanthrene derivative, and repeating unit n is an integer from 10 to 150.

상기의 다른 목적을 달성하기 위하여, 본 발명은In order to achieve the above another object, the present invention

본 발명에 따른 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 태양광 흡수 물질로서 포함하는 것을 특징으로 하는 유기 고분자 박막 태양전지를 제공한다. An organic polymer thin film solar cell comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to the present invention as a solar absorbing material.

본 발명의 4H-사이클로펜타[def]페난트렌의 골격을 갖는 공중합체는 넓은 태양광 흡수대역을 가질 뿐만 아니라 일반적인 유기용매에 잘 용해되어 상온 스핀코팅 공정이 가능하여 단순한 공정을 통해 구부림이 가능한 플라스틱 기판 위에 유기 고분자 박막 태양전지 소자 (organic polymer thin film solar cell)를 제작할 수 있는 훌륭한 장점을 가지고 있다.The copolymer having a skeleton of the 4 H -cyclopenta [ def ] phenanthrene of the present invention not only has a wide solar absorption band but also is well dissolved in a general organic solvent, allowing room temperature spin coating to be bent through a simple process. It has the great advantage of fabricating organic polymer thin film solar cell on plastic substrate.

본 발명은 하기 화학식 1로 표시되는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 제공한다:The present invention provides a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton represented by the following formula (1):

Figure 112008061868269-PAT00003
Figure 112008061868269-PAT00003

상기 식에서, A는 전자 수용체이고, D는 4H-사이클로펜타[def]페난트렌 유도체이고, 반복단위 n은 10 내지 150의 정수이다.Wherein A is an electron acceptor, D is a 4H -cyclopenta [ def ] phenanthrene derivative, and repeating unit n is an integer from 10 to 150.

상기 화학식 1에서 D로 표시되는 페난트렌 유도체는 하기 화학식 2 또는 화학식 3으로 표시될 수 있다:The phenanthrene derivative represented by D in Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3:

Figure 112008061868269-PAT00004
Figure 112008061868269-PAT00004

여기서, R1 및 R2는 각각 독립적으로 C1 -20의 선형 또는 가지형 알킬기이다.Wherein, R 1 and R 2 are each independently a linear or branched alkyl group of C 1 -20.

Figure 112008061868269-PAT00005
Figure 112008061868269-PAT00005

여기서, R1 및 R2는 각각 독립적으로 C1 -20의 선형 또는 가지형 알킬기이다.Wherein, R 1 and R 2 are each independently a linear or branched alkyl group of C 1 -20.

상기 화학식 1에서 A로 표시되는 전자 수용체는 하기 화학식 4로 표시될 수 있다:The electron acceptor represented by A in Formula 1 may be represented by Formula 4 below:

Figure 112008061868269-PAT00006
Figure 112008061868269-PAT00006

보다 구체적으로 상기 화학식 1은 하기 화학식 5 또는 화학식 6으로 표시될 수 있다.More specifically, Chemical Formula 1 may be represented by the following Chemical Formula 5 or Chemical Formula 6.

Figure 112008061868269-PAT00007
Figure 112008061868269-PAT00007

Figure 112008061868269-PAT00008
Figure 112008061868269-PAT00008

상기 식에서, 반복단위 n은 10 내지 150의 정수이다.In the above formula, repeating unit n is an integer of 10 to 150.

상기 유기 고분자는 4H-사이클로펜타[def]페난트렌 유도체를 전자공여체로, 다이(2-싸이엔일-2-일)-2,1,3-벤조싸이아다이아졸을 전자 수용체로 포함한다.The organic polymer includes a 4 H -cyclopenta [ def ] phenanthrene derivative as an electron donor and a di (2-thienyl-2-yl) -2,1,3-benzothiazole as an electron acceptor. .

본 발명의 일구현예에 따른 고분자는 새로운 백본인 4H-사이클로펜타[def]페난트렌 유도체를 전자 공여체로 다이(2-싸이엔일-2-일)-2,1,3-벤조싸이아다이아졸을 전자 수용체로 하여 기존의 태양전지용 고분자보다 좀더 장파장 쪽 흡수를 위한, 즉 기존의 고분자가 흡수하지 못하는 파장 대역의 빛을 흡수하는 특성이 나타 난다.The polymer according to one embodiment of the present invention is a new backbone, 4 H -cyclopenta [ def ] phenanthrene derivative, as an electron donor, as a di (2-thien-2-yl) -2,1,3-benzothia By using the diazole as an electron acceptor, it has a characteristic of absorbing light in a wavelength band that is longer than that of a conventional solar cell polymer, that is, that the conventional polymer does not absorb.

본 발명의 4H-사이클로펜타[def]페난트렌 유도체와 다이(2-싸이엔일-2-일)-2,1,3-벤조싸이아다이아졸 교대 고분자는 종래에 알려진 통상의 방법을 이용하여 합성될 수 있으며, 특별히 제한되는 것은 아니다. 보다 구체적으로, 상기 화학식 5와 화학식 6으로 표시되는 화합물은 하기 반응식 1과 2에 따라 합성될 수 있다.The 4H -cyclopenta [ def ] phenanthrene derivative of the present invention and the di (2-thienyl-2-yl) -2,1,3-benzothiadiazole alternating polymer can be prepared using conventional methods known in the art. It can be synthesized, and is not particularly limited. More specifically, the compounds represented by Formula 5 and Formula 6 may be synthesized according to the following Schemes 1 and 2.

폴리(2,6-((4,4-비스(2-에틸헥실)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸)))의 합성Poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy Yen-yl) - Synthesis of 2,1,3-benzothiadiazole)))

Figure 112008061868269-PAT00009
Figure 112008061868269-PAT00009

반응식 1에서 보는 바와 같이, 4H-사이클로펜타[def]페난트렌(화학식 1a)을 수소화 반응을 통하여 8,9-다이하이드로-4H-사이클로펜타[def]페난트렌(화학식 1b) 을 수득하고, 상기 8,9-다이하이드로-4H-사이클로펜타[def]페난트렌(화학식 1b)을 브롬화 반응을 통하여 2,6-다이브로모-8,9-다이하이드로-4H-사이클로펜타[def]페난트렌(화학식 1c)을 수득하고, 상기 2,6-다이브로모-8,9-다이하이드로-4H-사이클로펜타[def]페난트렌(화학식 1c)을 브로민과 반응시켜 2,6-다이브로모-4H-사이클로펜타[def]페난트렌(화학식 1d)을 수득하고, 상기 2,6-다이브로모-4H-사이클로펜타[def]페난트렌(화학식 1d)과 2-에틸헥실브로마이드를 수산화나트륨과 반응시켜 2,6-다이브로모-4,4-비스-(2-에틸헥실)-4H-사이클로펜타[def]페난트렌 (화학식 1e)을 수득하고, 상기 2,6-다이브로모-4,4-비스-(2-에틸헥실)-4H-사이클로펜타[def]페난트렌 (화학식 1e)을 비스(피나콜라토)다이보론과 반응시켜 4,4-비스(2-에틸헥실)-2,6-비스(4′,4′,5′,5′-테트라메틸-1′,3′,2′-다이옥사보로렌-2′-일)-4H-사이클로펜타[def]페난트렌 (화학식 1f)을 수득하고, 상기 4,4-비스(2-에틸헥실)-2,6-비스(4′,4′,5′,5′-테트라메틸-1′,3′,2′-다이옥사보로렌-2′-일)-4H-사이클로펜타[def]페난트렌 (화학식 1f)와 4,7-비스(5-브로모-2-싸이엔일)-2,1,3-벤조싸이아다이아졸 (화학식 1h)을 스즈끼 커플링 반응을 통하여 폴리(2,6-((4,4-비스(2-에틸헥실)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸))) (화학식 1g)를 수득한다. As shown in Scheme 1, 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1b) was obtained through hydrogenation of 4H -cyclopenta [ def ] phenanthrene (Formula 1a). , 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] through bromination of the 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1b) A phenanthrene (Formula 1c) was obtained and the 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1c) was reacted with bromine to give 2,6-dive Obtain lomo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d), and hydroxylate the 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d) with 2-ethylhexylbromide It is reacted with sodium 2,6-dibromo-4,4-bis (2-ethylhexyl) -4 H - to give the cyclopenta [def] phenanthrene (formula 1e), wherein the 2,6-dibromo- 4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene (Formula 1e) 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 Tren (Formula 1f) was obtained and the 4,4-bis (2-ethylhexyl) -2,6-bis (4 ′, 4 ′, 5 ′, 5′-tetramethyl-1 ′, 3 ′, 2 '- dioxane Sabo Lauren-2'-yl) -4 H-cyclopenta [def] phenanthrene (formula 1f) and 4,7-bis (5-bromo-2-Im yen yl) -2,1,3 - benzothiazol Oh oxadiazole (formula 1h) via a Suzuki coupling reaction of poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt -((4,7-di ((2-thienyl) -2,1,3-benzothiadiazole))) (Formula 1 g) is obtained.

폴리(2,6-(4,4-비스(4-((2-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸)))의 합성Poly (2,6- (4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di (( Synthesis of 2-thienyl) -2,1,3-benzothiadiazole)))

Figure 112008061868269-PAT00010
Figure 112008061868269-PAT00010

반응식 2에서 보는 바와 같이, 2,6-다이브로모-4H-사이클로펜타[def]페난트렌 (화학식 1d)을 산화반응을 통하여 2,6-다이브로모-4H-사이클로펜타[def]페난트렌-4-온 (화학식 2a)을 수득하고, 상기 2,6-다이브로모-4H-사이클로펜타[def]페난트렌-4-온 (화학식 2a)을 페놀, 염화아연(II), 염화수소 가스와 반응시켜 2,6-다이브로모-4,4-비스(4'-하이드록시페닐)-4H-사이클로펜타[def]페난트렌 (화학식 2b)을 수득하고, 상기 2,6-다이브로모-4,4-비스(4'-하이드록시페닐)-4H-사이클로펜타[def]페난트렌 (화학식 2b)을 2-에틸헥실브로마이드와 반응시켜 2,6-다이브로모-4,4-비스(4-((2-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트렌 (화학식 2c)를 수득하고, 상기 2,6-다이브로모-4,4-비스(4-((2-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트렌 (화학식 2c)을 비스(피나콜라토)다이보론과 반응시켜 4,4-비 스(4-((2-에틸헥실)옥시)페닐)-2,6-비스(4',4',5',5'-테트라메틸-1',3',2'-다이옥사보로렌-2'-일)-4H-사이클로펜타[def]페난트렌 (화학식 2d)을 수득하고, 상기 4,4-비스(4-((2-에틸헥실)옥시)페닐)-2,6-비스(4',4',5',5'-테트라메틸-1',3',2'-다이옥사보로렌-2'-일)-4H-사이클로펜타[def]페난트렌 (화학식 2d)와 4,7-비스(5-브로모-2-싸이엔일)-2,1,3-벤조싸이아다이아졸 (화학식 1g)을 스즈끼 커플링 반응을 통하여 폴리(2,6-(4,4-비스(4-((2-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸))) (화학식 2e)를 수득한다.As shown in Scheme 2, 2,6-dibromo -4 H-cyclopenta [def] phenanthrene (Formula 1d) of 2,6-dibromo -4 H through the oxidation-cyclopenta [def] phenanthrene 4-one (Formula 2a) was obtained, and the 2,6-dibromo- 4H -cyclopenta [ def ] phenanthren-4-one (Formula 2a) was mixed with phenol, zinc chloride (II), and hydrogen chloride gas. reacting 2,6-dibromo-4,4-bis (4'-hydroxyphenyl) -4 H - cyclopenta [def] phenanthrene (formula 2b) of the 2,6-dibromo-4, to give , 4-bis (4'-hydroxyphenyl) -4 H - cyclopenta [def] phenanthrene (formula 2b) was reacted with 2-ethylhexyl bromide and 2,6-dibromo-4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene give the (formula 2c), and wherein the 2,6-dibromo-4,4-bis (4 - ((2 -ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene (formula 2c) of bis (pinacolato 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 (formula 2d) to obtain, and the 4,4-bis (4 - ((2-ethylhexyl )) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lauren-2'-yl) -4 H - cyclopenten Suzuki coupling reaction between penta [ def ] phenanthrene (Formula 2d) and 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole (Formula 1g) via a poly (2,6- (4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ( (2-thienyl) -2,1,3-benzothiadiazole))) is obtained by formula (2e).

또한, 본 발명은 상기 유기 고분자(4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체)를 광흡수 물질로 이용하는 유기 고분자 박막 태양전지 소자, 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 발광 물질로서 이용하는 유기 전기 발광 소자, 유기 반도체 물질로 이용하는 유기 박막 트랜지스터를 제공한다.The present invention also provides an organic polymer thin film solar cell device using the organic polymer (copolymer having a 4H -cyclopenta [ def ] phenanthrene skeleton) as a light absorbing material, and a 4H -cyclopenta [ def ] phenanthrene skeleton. An organic electroluminescent element using a copolymer having a light emitting material and an organic thin film transistor using an organic semiconductor material are provided.

이하, 실시예를 참고로 하여 본 발명을 보다 상세하게 설명한다. 하기의 실시예는 본 발명을 구체적으로 설명하려는 것이며, 하기의 실시예에 의하여 본 발명의 범위가 제한되지는 않는다.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.

실시예Example

실시예Example 1 One

폴리(2,6-((4,4-Poly (2,6-((4,4- 비스Vis (2-(2- 에틸헥실Ethylhexyl )-4)-4 HH -사이클로펜타[Cyclopenta [ defdef ]페난트렌)-] Phenanthrene)- altalt - ((4,7-다이((2--((4,7-die ((2- 싸이엔일Cynyl )-2,1,3-) -2,1,3- 벤조싸이아다이아졸Benzothiadiazole )))의 제조Manufacture of)))

1) 8,9-다이하이드로-4H-사이클로펜타[def]페난트렌 (화학식 1b)의 합성1) Synthesis of 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1b)

4H-사이클로펜타[def]페난트렌 (화학식 1a) 1.0 g (5.3 mmol)과 10% 팔라듐/탄소 0.50 g을 메탄올 20 ml에 녹인 후 수소 기체 하에서 상온에서 20 시간 교반하였다. 촉매를 거른 후 용매를 진공증류한 후 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 0.90 g (87%)의 흰색 고체를 얻었다.1.0 g (5.3 mmol) and 100 palladium / carbon 0.50 g of 4H -cyclopenta [ def ] phenanthrene (Formula 1a) 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. 0.90 g (87%) of a white solid was obtained.

R f = 0.8 (SiO2, 헥산100%)R f = 0.8 (SiO 2 , hexane100%)

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

1H NMR (300 MHz, CDCl3) δ7.37 (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) 1 H NMR (300 MHz, CDCl 3 ) δ7.37 (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)

13C NMR (75 MHz, CDCl3) δ140.67, 139.65, 130.76, 127.51, 124.92, 122.95, 37.69, 26.51 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, C15H12, 192.0943 (calcd. 192.0939)HRMS, m / e, C 15 H 12 , 192.0943 (calcd. 192.0939)

2) 2,6-다이브로모-8,9-다이하이드로-4H-사이클로펜타[def]페난트렌 (화학식 1c)의 합성2) Synthesis of 2,6-Dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1c)

이렇게 수득한 화학식 1b의 화합물 0.90 g (4.6 mmol)을 사염화탄소 80 ml에 녹인 후 이브롬화구리산화알루미늄 착물 12 g 첨가한 후 80℃에서 5시간 교반하였다. 고체를 거른 후 용매를 진공증류한 후 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 1.5 g (93%)의 엷은 노란색 고체를 얻었다.0.90 g (4.6 mmol) of the compound of Formula 1b thus obtained was dissolved in 80 ml of carbon tetrachloride, and then 12 g of aluminum tribromide 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. 1.5 g (93%) of a pale yellow solid was obtained.

R f = 0.5 (SiO2, 헥산 100%)R f = 0.5 (SiO 2 , hexane 100%)

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

1H NMR (300 MHz, CDCl3) δ 7.47 (s, 2H), 7.46 (s, 2H), 3.83 (s, 2H), 3.08 (s, 4H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.47 (s, 2H), 7.46 (s, 2H), 3.83 (s, 2H), 3.08 (s, 4H)

13C NMR (75 MHz, CDCl3) δ 141.81, 137.56, 131.91, 128.43, 126.43, 121.33, 37.35, 25.95 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, C15H10Br2, 347.9153 (calcd. 347.9149)HRMS, m / e, C 15 H 10 Br 2 , 347.9153 (calcd. 347.9149)

3) 2,6-다이브로모-4H-사이클로펜타[def]페난트렌 (화학식 1d)의 합성3) Synthesis of 2,6-Dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d)

이렇게 수득한 화학식 1c의 화합물 1.5 g (4.3 mmol)을 카본 다이설파이드 30 ml에 녹인 후 상온에서 브로민 0.27 ml (5.2 mmol)을 2시간 동안 천천히 첨가한 후 1시간 교반하였다. 용매를 진공증류한 후 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 1.2 g (80%)의 엷은 노란색 고체를 얻었다. 1.5 g (4.3 mmol) of the compound of Chemical Formula 1c thus obtained was dissolved in 30 ml of carbon disulfide, and 0.27 ml (5.2 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 (SiO2, 헥산 100%)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, 688FT-IR (KBr, cm -1 ): 3043, 2926, 1570, 1419, 1403, 1309, 1211, 1063, 863, 831, 808, 711, 688

1H NMR (300 MHz, CDCl3) δ 7.99 (s, 2H), 7.80 (s, 2H), 7.75 (s, 2H), 4.32 (s, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.99 (s, 2H), 7.80 (s, 2H), 7.75 (s, 2H), 4.32 (s, 2H)

13C NMR (75 MHz, CDCl3) δ 143.03, 132.91, 128.97, 127.97, 126.41, 125.62, 125.31, 37.16 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, C15H8Br2, 345.8993 (calcd. 345.8993)HRMS, m / e, C 15 H 8 Br 2 , 345.8993 (calcd. 345.8993)

4) 2,6-다이브로모-4,4-비스-(2-에틸헥실)-4H-사이클로펜타[def]페난트렌 (화학식 1e)의 합성Synthesis of the cyclopenta [def] phenanthrene (Formula 1e) - 4) 2,6- dibromo-4,4-bis (2-ethylhexyl) -4 H

이렇게 수득한 화학식 1d의 화합물 3.1 g (9.0 mmol)과 촉매량의 트라이에틸벤질암모늄 클로라이드를 다이메틸설폭사이드 175ml에 녹인 후 2-에틸헥실브로마이드 4.8 ml (27 mmol)를 첨가하였다. 60 ℃에서 1시간 교반후 50% 수산화나트륨 수용액 10 ml를 첨가하고 상온에서 5시간 교반하였다. 과량의 에틸아세테이트를 첨가하여 수산화나트륨 침전을 형성시키고 거른 후 유기층을 증류수로 추출하였다. 용매를 진공증류한 후 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 3.6 g (70%)의 흰색 결정을 얻었다.3.1 g (9.0 mmol) of the compound of Chemical Formula 1d and a catalytic amount of triethylbenzylammonium chloride were dissolved in 175 ml of dimethyl sulfoxide, and 4.8 ml (27 mmol) of 2-ethylhexyl bromide was added thereto. After stirring at 60 ° C. for 1 hour, 10 ml of 50% aqueous sodium hydroxide solution was added thereto, and the mixture was 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. 3.6 g (70%) of white crystals were obtained.

R f = 0.6 (SiO2, 헥산 100%)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, 1066FT-IR (KBr, cm -1 ): 3046, 2959, 2926, 2872, 2858, 2728, 1909, 1744, 1593, 1577, 1460, 1416, 1390, 1379, 1367, 1306, 1222, 1213, 1066

1H NMR (300 MHz, CDCl3) δ7.95(s, 2H), 7.74(s, 2H), 7.64 (s, 2H), 2.17 (d, 4H, J = 5.1 Hz), 0.87-0.47 (m, 30H) 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)

13C NMR (75 MHz, CDCl3) δ150.97, 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 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, C31H40 79Br79Br, 570.1532 (calcd. 570.1497), C31H40 79Br81Br, 572.1495 (calcd. 572.1476), C31H40 81Br81Br, 574.1454 (calcd. 574.1456)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-비스(2-에틸헥실)-2,6-비스(4′,4′,5′,5′-테트라메틸-1′,3′,2′-다이옥사보로렌-2′-일)-4H-사이클로펜타[def]페난트렌 (화학식 1f)의 합성5) 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 1f)

이렇게 수득한 화학식 11e의 화합물 2.2 g (3.8 mmol)과 비스(피나콜라토)다이보론 4.9 g (19 mmol)과 포타슘아세테이트 2.3 g (23 mmol)를 N,N-다이메틸포름아마이드 40ml에 녹인 후 상온에서 1,1'-비스(다이페닐포스피노)페로센팔라듐(II)다이클로로 다이클로로메탄 착물 0.18 g (0.23 mmol)을 첨가한 후 60 ℃에서 12 시 간 교반하였다. 에테르와 증류수로 추출하고 마그네슘설파이트로 건조한 후 용매를 진공증류하여 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 2.0 g (78%)의 흰색 결정을 얻었다.2.2 g (3.8 mmol) of the compound of formula 11e, 4.9 g (19 mmol) of bis (pinacolato) diboron and 2.3 g (23 mmol) of potassium acetate were dissolved in 40 ml of N , N -dimethylformamide. 0.18 g (0.23 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. 2.0 g (78%) of white crystals were obtained.

R f = 0.42 (SiO2, 에틸아세테이트:헥산 = 1:20)R f = 0.42 (SiO 2 , ethyl acetate: hexane = 1:20)

1H NMR (300 MHz, CDCl3) 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) 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)

13C NMR (75 MHz, CDCl3) 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 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, C43H64B2O4, 666.4996 (calcd. 666.5005)HRMS, m / e, C 43 H 64 B 2 O 4 , 666.4996 (calcd. 666.5005)

6) 폴리(2,6-((4,4-비스(2-에틸헥실)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸))) (화학식 1e)의 합성6) a poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy Yen days ) -2,1,3-benzothiadiazole))) Synthesis of Formula 1e)

이렇게 수득한 화학식 1f의 화합물 0.29 g (0.43 mmol)과 화학식 1h의 화합물 0.22 g (0.43 mmol)과 2M 포타슘카보네이트 수용액 2.1 ml와 테트라키스(트라이페닐포스핀) 팔라듐(0) 15 mg (0.013 mmol)을 톨루엔 11 ml에 녹인 후 80 ℃에서 4 일간 교반하였다. 용액을 메탄올 500 ml에 천천히 첨가한 뒤 생성된 고체를 여과, 세척, 건조하여 원하는 생성물 폴리(2,6-((4,4-비스(2-에틸헥실)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸))) 100mg을 얻었다.Thus obtained 0.29 g (0.43 mmol) of the compound of Formula 1f, 0.22 g (0.43 mmol) of the compound of Formula 1h, 2.1 ml of an aqueous 2M potassium carbonate solution and 15 mg (0.013 mmol) of tetrakis (triphenylphosphine) palladium (0) Was dissolved in 11 ml of toluene and stirred at 80 ° C. for 4 days. The solution was filtered after the resultant solid was slowly added to 500 ml of methanol, washed, and dried to the desired product of poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy yen-yl) -2,1,3- oxadiazole benzothiazol O)) of the target compound) 100mg.

실시예Example 2 2

폴리(2,6-(4,4-Poly (2,6- (4,4- 비스Vis (4-((2-(4-((2- 에틸헥실Ethylhexyl )) 옥시Oxy )) 페닐Phenyl )-4)-4 HH -사이클로펜타[Cyclopenta [ defdef ]페난트렌)-] Phenanthrene)- altalt -((4,7--((4,7- 다이die ((2-((2- 싸이엔일Cynyl )-2,1,3-) -2,1,3- 벤조싸이아다이아졸Benzothiadiazole )))의 제조Manufacture of)))

1) 2,6-다이브로모-4H-사이클로펜타[def]페난트렌-4-온 (화학식 2a)의 합성1) Synthesis of 2,6-Dibromo- 4H -cyclopenta [ def ] phenanthren-4-one (Formula 2a)

2,6-다이브로모-4H-사이클로펜타[def]페난트렌 (화학식 1d) 1.2 g (3.5 mmol)을 벤젠 100 ml에 녹인 후 85% 이산화망간(IV) 5.0 g (58 mmol)을 첨가하고 80 ℃에서 12 시간 교반하였다. 용매를 진공증류하여 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 1.0 g (80%)의 노란색 고체를 얻었다.1.2 g (3.5 mmol) of 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d) was dissolved in 100 ml of benzene, followed by addition of 5.0 g (58 mmol) of 85% manganese dioxide (IV). It stirred at 12 degreeC. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 1.0 g (80%) of a yellow solid was obtained.

R f = 0.2 (SiO2, 헥산 100%)R f = 0.2 (SiO 2 , hexane 100%)

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

1H NMR (300 MHz, CDCl3) δ 8.10 (s, 2H), 7.90 (s, 2H), 7.72 (s, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.10 (s, 2H), 7.90 (s, 2H), 7.72 (s, 2H)

13C NMR (75 MHz, Benzene-d6) δ 190.08, 137.89, 133.97, 129.52, 126.79, 126.72, 125.14, 124.27 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, C15H6 79Br79BrO, 359.8781 (calcd. 359.8785)HRMS, m / e, C 15 H 6 79 Br 79 BrO, 359.8781 (calcd. 359.8785)

2) 2,6-다이브로모-4,4-비스(4'-하이드록시페닐)-4H-사이클로펜타[def]페난트렌 (화학식 2b)의 합성Synthesis of the cyclopenta [def] phenanthrene (formula 2b) - 2) 2,6- dibromo-4,4-bis (4'-hydroxyphenyl) -4 H

이렇게 수득한 화학식 2a의 화합물 1.0 g (2.8 mmol)과 페놀 20 ml와 염화아연(II) 0.76 g (5.6 mmol)에 50 ℃에서 염산가스를 3 시간 주입한 후 관 크로마토그래피를 통하여 생성물을 분리하였다. 1.2 g (84%)의 흰색 고체를 얻었다.1.0 g (2.8 mmol) of the compound of Formula 2a, 20 ml of phenol and 0.76 g (5.6 mmol) of zinc chloride (II) were injected at 50 ° C. for 3 hours, and the product was separated by column chromatography. . 1.2 g (84%) of a white solid were obtained.

R f = 0.2 (SiO2, 에틸아세테이트:헥산 = 1:3)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, 707FT-IR (KBr, cm -1 ): 3853, 3648, 3277, 3032, 1574, 1508, 1230, 1066, 899, 858, 762, 707

1H 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) 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)

13C 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 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, C27H16 79Br79BrO2, 529.9518 (calcd. 529.9517)HRMS, m / e, C 27 H 16 79 Br 79 BrO 2 , 529.9518 (calcd. 529.9517)

3) 2,6-다이브로모-4,4-비스(4'-((2"-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트 (화학식 2c)의 합성Synthesis of the cyclopenta [def] phenanthrene (Formula 2c) - 3), 2,6- dibromo-4,4-bis (4 '- ((2' - ethylhexyl) oxy) phenyl) -4 H

이렇게 수득한 화학식 2b의 화합물 1.2g (2.3 mmol)을 아세톤 100 ml에 녹이고 요오드화 나트륨 0.35 g (2.3 mmol)과 세슘카보네이트 4.9 g (1.4 mmol)과 2-에틸헥실브로마이드 1.7 ml (9.3 mmol)를 첨가한 후 70 ℃에서 24 시간 교반하였다. 용매를 진공증류하여 생기는 고체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 0.46 g (26%)의 흰색 고체를 얻었다.1.2 g (2.3 mmol) of the compound of Formula 2b thus obtained was dissolved in 100 ml of acetone, and 0.35 g (2.3 mmol) of sodium iodide, 4.9 g (1.4 mmol) of cesium carbonate, and 1.7 ml (9.3 mmol) of 2-ethylhexylbromide were added thereto. After stirring at 70 ° C. 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 were obtained.

R f = 0.74 (SiO2, 헥산 100%)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, 729FT-IR (KBr, cm -1 ): 3750, 2960, 2930, 2850, 1610, 1580, 1510, 1470, 1410, 1300, 1280, 1170, 1030, 854, 764, 729

1H NMR (300 MHz, CDCl3) 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) 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)

13C NMR (75 MHz, CDCl3) 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 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, C43H48 79Br79BrO2, 754.2000 (calcd. 754.2021)HRMS, m / e, C 43 H 48 79 Br 79 BrO 2 , 754.2000 (calcd. 754.2021)

4) 4,4-비스(4-((2-에틸헥실)옥시)페닐)-2,6-비스(4',4',5',5'-테트라메틸-1',3',2'-다이옥사보로렌-2'-일)-4H-사이클로펜타[def]페난트렌 (화학식 2d)의 합성4) 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 2d) - dioxane Sabo Lauren-2'-yl) -4 H

이렇게 수득한 화학식 2c의 화합물 0.72 g (0.95 mmol)과 비스(피나콜라토)다이보론 1.2 g (4.8 mmol)과 포타슘아세테이트 0.47 g (4.8 mmol)을 N,N-다이메틸포름아마이드 40ml에 녹인 후 상온에서 1,1'-비스(다이페닐포스피노)페로센팔라듐(II)다이클로로 다이클로로메탄 착물 50 mg (0.050 mmol)을 첨가한 후 60 ℃에서 12 시간 교반하였다. 에테르와 증류수로 추출하고 마그네슘설파이트로 건조한 후 용매를 진공증류하여 생기는 액체성 잔류물을 관 크로마토그래피를 통하여 생성물을 분리하였다. 0.70 g (87 %)의 노란색 액체를 얻었다.0.72 g (0.95 mmol) of the compound of formula 2c, 1.2 g (4.8 mmol) of bis (pinacolato) diboron and 0.47 g (4.8 mmol) of potassium acetate were dissolved in 40 ml of N , N -dimethylformamide. At room temperature, 50 mg (0.050 mmol) of 1,1′-bis (diphenylphosphino) ferrocenepalladium (II) dichloro dichloromethane complex were added, 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. 0.70 g (87%) of yellow liquid was obtained.

R f = 0.36 (SiO2, 에틸아세테이트:헥산 = 1:20)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, 525FT-IR (KBr, cm -1 ): 3744, 2914, 2852, 1617, 1521, 1469, 1381, 1328, 1245, 1130, 1020, 951, 841, 718, 525

1H NMR (300 MHz, CDCl3) 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) 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)

13C NMR (75 MHz, CDCl3) 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, 14.32, 11.35 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, C55H72Br2O6, 850.5507 (calcd. 850.5515)HRMS, m / e, C 55 H 72 Br 2 O 6 , 850.5507 (calcd. 850.5515)

5) 폴리(2,6-(4,4-비스(4-((2-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸))) (화학식 2e)의 합성5) a poly (2,6- (4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- dimethyl Synthesis of ((2-thienyl) -2,1,3-benzothiadiazole)))

이렇게 수득한 화학식 2d의 화합물 0.32 g (0.38 mmol)과 화학식 1h의 화합물 0.19 g (0.38 mmol)과 2M 포타슘카보네이트 수용액 1.9 ml와 테트라키스(트라이페닐포스핀) 팔라듐(0) 13 mg (0.011 mmol)을 톨루엔 11 ml에 녹인 후 80 ℃에서 4 일간 교반하였다. 용액을 메탄올 500 ml에 천천히 첨가한 뒤 생성된 고체를 여과, 세척, 건조하여 원하는 생성물 폴리(2,6-(4,4-비스(4-((2-에틸헥실)옥시)페닐)-4H-사이클로펜타[def]페난트렌)-alt-((4,7-다이((2-싸이엔일)-2,1,3-벤조싸이아다이아졸))) 100mg을 얻었다.0.32 g (0.38 mmol) of the compound of Formula 2d, 0.19 g (0.38 mmol) of the compound of Formula 1h, 1.9 ml of a 2M potassium carbonate solution, and 13 mg (0.011 mmol) of tetrakis (triphenylphosphine) palladium (0) Was dissolved in 11 ml of toluene 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 (2,6- (4,4-bis (4-((2-ethylhexyl) oxy) phenyl) -4 H - cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy yen-yl) -2,1,3- oxadiazole benzothiazol O)) of the target compound) 100mg.

실시예 1 및 실시예 2에서 합성하여 제조한 고분자들은 유기용매에 대한 좋은 용해도를 가져 일반적인 유기용매에 완전히 용해되었다. GPC를 이용하여 분자량 을 측정하며, 측정된 분자량은 수평균 분자량이 5,000이고, 질량평균 분자량이 8,000이며, 분산도가 1.6이다. 이 고분자들은 530 nm 근처에서 최대흡수를 나타내었다.The polymers synthesized in Examples 1 and 2 had good solubility in organic solvents and were completely dissolved in general organic solvents. The molecular weight was measured using GPC, and the measured molecular weight was 5,000, number average molecular weight, 8,000 mass average molecular weight, and dispersion degree 1.6. These polymers exhibited maximum absorption near 530 nm.

도 1은 이 고분자들을 태양광 흡수층으로 이용한 유기 고분자 박막 태양전지 소자의 단면도로서, 유리 상에 코팅된 ITO와 알류미늄(Al)을 각각 음극과 양극으로 하여 박막 태양전지 소자를 제작한 것이다.FIG. 1 is a cross-sectional view of an organic polymer thin film solar cell device using these polymers as a solar absorption layer. A thin film solar cell device is fabricated by using ITO and aluminum (Al) coated on glass as a cathode and an anode, respectively.

실시예Example 3 3

유기 고분자 박막 태양전지 소자의 제조Fabrication of Organic Polymer Thin Film Solar Cell Devices

유리 기판(1) 상부에 인듐 틴 옥사이드 (ITO)의 반투명 전극 (semitransparent electrode) (2)을 형성하고 상기 반투명 전극 (semitransparent electrode)(2) 상부에 50 nm 두께의 전도성 고분자(Baytron P, H. C. Starck) 정공 수송층 (hole transporting layer) (3)을 형성하였다.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.

상기 정공 수송층 (3) 상부에 상기 실시예 1 및 2 에서 제조한 고분자들과 [6,6]-phenyl-C61-butyric acid methylester (PCBM) 을 1:4 (w/w) 혼합하여 스핀 코팅에 의해 100nm 두께의 태양광 흡수 유기 반도체층(4)을 형성하고, 상기 유기 반도체층(4) 상부에 알루미늄을 사용하여 알루미늄 (Al) 금속 전극 (5)을 형성함으로써 광전 효율 측정을 위한 소자를 제작하였다. The polymers prepared in Examples 1 and 2 and [6,6] -phenyl-C61-butyric acid methylester (PCBM) were mixed 1: 4 (w / w) on the hole transport layer 3 to spin coating. To form a 100 nm-thick photovoltaic organic semiconductor layer 4 and to form an aluminum (Al) metal electrode 5 using aluminum on the organic semiconductor layer 4 to fabricate a device for measuring photoelectric efficiency. It was.

평가 및 결과Evaluation and Results

도 2는 실시예 1에서 제조한 고분자를 이용하여 제작한 유기 고분자 박막 태양전지 소자의 흡수 스펙트럼을 도시한다. 도 2를 참조하면, 실시예 1에서 제조한 고분자를 이용함으로써 가시광선 영역에서 넓은 광흡수 스펙트럼 대역을 나타내고 있다. 본 발명에 의하면, 종래의 태양전지용 고분자보다 좀더 장파장 쪽 흡수를 위한, 즉 기존의 고분자가 흡수하지 못하는 파장 대역의 빛을 흡수하는 특성이 나타난다.FIG. 2 shows an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 1. FIG. Referring to Figure 2, by using the polymer prepared in Example 1 shows a broad light absorption spectrum band in the visible light region. According to the present invention, a characteristic of absorbing light in a wavelength band that is absorbed by a longer wavelength than that of a conventional solar cell polymer, that is, a conventional polymer does not appear.

도 3은 이렇게 제작된 소자는 A.M. 1.5 조건에서 광전 효율을 측정하여 도시한다. 도 3으로부터 계산된 광전 효율은 100 mW/cm2의 빛에서 1.00%로 나타났다.FIG. 3 shows the device fabricated in this way by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 3 was found to be 1.00% at 100 mW / cm 2 light.

도 4는 실시예 2에서 제조한 고분자를 이용하여 제작한 유기 고분자 박막 태양전지 소자의 흡수 스펙트럼을 도시하다. 도 4를 참조하면, 실시예 2에서 제조한 고분자를 이용함으로써 가시광선 영역에서 넓은 광흡수 스펙트럼 대역을 나타내고 있다. 본 발명에 의하면, 종래의 태양전지용 고분자보다 좀더 장파장 쪽 흡수를 위한, 즉 기존의 고분자가 흡수하지 못하는 파장 대역의 빛을 흡수하는 특성이 나타난다.4 illustrates an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 2. FIG. Referring to Figure 4, by using the polymer prepared in Example 2 shows a wide light absorption spectrum band in the visible light region. According to the present invention, a characteristic of absorbing light in a wavelength band that is absorbed by a longer wavelength than that of a conventional solar cell polymer, that is, a conventional polymer does not appear.

이와 같이 제작된 소자는 A.M. 1.5 조건에서 광전 효율을 측정하여 도 5에 도시하였다. 도 3으로부터 계산된 광전 효율은 100 mW/cm2의 빛에서 1.12%로 나타났다. The device manufactured as described above is illustrated in FIG. 5 by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 3 was found to be 1.12% at 100 mW / cm 2 light.

도 6은 실시예 2에서 제조한 고분자를 이용하여 제작한 유기 박막 트랜지스터의 전압, 전류밀도 실험결과를 나타낸다. 도 6을 참조하면, 전압의 증가에 따라 전류밀도가 증가하는 전형적인 반도체의 특성을 나타낸다. 따라서 본 발명에 따른 고분자를 유기 박막 트랜지스터의 반도체 물질로 할 수 있음을 알 수 있다.6 shows voltage and current density test results of an organic thin film transistor manufactured using the polymer prepared in Example 2. FIG. Referring to FIG. 6, the characteristics of a typical semiconductor in which current density increases with increasing voltage is shown. Therefore, it can be seen that the polymer according to the present invention can be used as a semiconductor material of an organic thin film transistor.

본 발명에 따른 고분자 화합물은 소자 적용 시에 스핀 코팅 공정이 가능하고 우수한 전기전도성, 유기 전기 발광 및 광기전력 특성을 제공할 수 있어 유기 고분자 태양전지, 유기 박막 트랜지스터, 유기 전기 발광 소자에 응용할 수 있다. 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 the spin coating process is possible when the device is applied and it can provide excellent electrical conductivity, organic electroluminescence, and photovoltaic characteristics. .

도 1은 본 발명에 따른 고분자를 이용한 유기 고분자 박막 태양전지 소자의 단면도이다.1 is a cross-sectional view of an organic polymer thin film solar cell device using a polymer according to the present invention.

도 2는 실시예 1의 고분자를 이용한 유기 고분자 박막 태양전지 소자의 흡수 스펙트럼을 도시한 그래프이다.FIG. 2 is a graph illustrating an absorption spectrum of an organic polymer thin film solar cell device using the polymer of Example 1. FIG.

도 3은 실시예 1의 고분자를 이용한 유기 고분자 박막 태양전지 소자의 광전효율 측정을 도시한 그래프이다.3 is a graph illustrating photoelectric efficiency measurement of an organic polymer thin film solar cell device using the polymer of Example 1. FIG.

도 4는 실시예 2에서 제조한 고분자를 이용하여 제조한 유기 고분자 박막 태양전지 소자의 흡수 스펙트럼을 도시한 그래프이다.4 is a graph showing an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 2. FIG.

도 5는 실시예 2의 고분자를 이용한 유기 고분자 박막 태양전지 소자의 흡수 스펙트럼을 도시한 그래프이다.FIG. 5 is a graph illustrating an absorption spectrum of an organic polymer thin film solar cell device using the polymer of Example 2. FIG.

도 6은 실시예 2의 고분자를 이용하여 제작한 유기 박막 트랜지스터의 전압, 전류밀도 실험결과를 도시한 그래프이다. FIG. 6 is a graph illustrating voltage and current density test results of an organic thin film transistor manufactured using the polymer of Example 2. FIG.

<도면의 주요 부분에 대한 부호 설명><Description of the symbols for the main parts of the drawings>

1: 기판 2: 반투명 전극1: substrate 2: translucent electrode

3: 정공 수송층 4: 태양광 흡수 유기 반도체층3: hole transport layer 4: solar absorption organic semiconductor layer

5: 금속 전극5: metal electrode

Claims (10)

하기 화학식 1로 표시되는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공줍합체:Co-polymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton represented by Formula 1 below: <화학식 1><Formula 1>
Figure 112008061868269-PAT00011
Figure 112008061868269-PAT00011
 상기 식에서, A는 전자 수용체이고, D는 4H-사이클로펜타[def]페난트렌 유도체이고, n은 10 내지 150이다.Wherein A is an electron acceptor, D is a 4H -cyclopenta [ def ] phenanthrene derivative, and n is from 10 to 150. 제1항에 있어서, 상기 D는 화학식 2 또는 화학식 3으로 표시되는 화합물인 것을 특징으로 하는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체:The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein D is a compound represented by Formula 2 or Formula 3. <화학식 2><Formula 2>
Figure 112008061868269-PAT00012
또는
Figure 112008061868269-PAT00012
or <화학식 3><Formula 3>
Figure 112008061868269-PAT00013
Figure 112008061868269-PAT00013
 여기서, R1 및 R2는 각각 독립적으로 C1 -20의 선형 또는 가지형 알킬기이다.Wherein, R 1 and R 2 are each independently a linear or branched alkyl group of C 1 -20. 제1항에 있어서, 상기 A는 하기 화학식 4로 표시되는 화합물인 것을 특징으로 하는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체:The copolymer having a 4H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein A is a compound represented by the following Chemical Formula 4: <화학식 4><Formula 4>
Figure 112008061868269-PAT00014
Figure 112008061868269-PAT00014
 제1항에 있어서, 수평균 분자량이 3,000 내지 6,000이고, 질량평균 분자량이 7,000 내지 10,000인 것을 특징으로 하는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체.The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein the number average molecular weight is 3,000 to 6,000 and the mass average molecular weight is 7,000 to 10,000. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물이 하기 화학식 5로 표시되는 것을 특징으로 하는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체:The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 5. <화학식 5><Formula 5>
Figure 112008061868269-PAT00015
Figure 112008061868269-PAT00015
 상기 식에서, 반복단위 n은 10 내지 150의 정수이다.In the above formula, repeating unit n is an integer of 10 to 150. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물이 하기 화학식 6으로 표시되는 것을 특징으로 하는 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체:The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 6. <화학식 6><Formula 6>
Figure 112008061868269-PAT00016
Figure 112008061868269-PAT00016
 상기 식에서, 반복단위 n은 10 내지 150의 정수이다.In the above formula, repeating unit n is an integer of 10 to 150. 제1항 내지 제6항 중 어느 한 항에 따른 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 태양광 흡수 물질로서 포함하는 것을 특징으로 하는 유기 고분 자 박막 태양전지.An organic polymer thin film solar cell comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to any one of claims 1 to 6 as a solar absorbing material. 제7항에 있어서, 상기 태양광 흡수 물질은 스핀코팅법을 이용하여 박막화되는 것을 특징으로 하는 유기 고분자 박막 태양전지.The organic polymer thin film solar cell of claim 7, wherein the solar light absorbing material is thinned by using a spin coating method. 제1항 내지 제6항 중 어느 한 항에 따른 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 유기 반도체 물질로서 포함하는 것을 특징으로 하는 유기 박막 트랜지스터.An organic thin film transistor comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to any one of claims 1 to 6 as an organic semiconductor material. 제1항 내지 제6항 중 어느 한 항에 따른 4H-사이클로펜타[def]페난트렌 골격을 갖는 공중합체를 발광 물질로서 포함하는 것을 특징으로 하는 유기 전기 발광 소자.An organic electroluminescent device comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to any one of claims 1 to 6 as a light emitting material.
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KR101540297B1 (en) * 2014-04-18 2015-07-30 부산대학교 산학협력단 Polymer with alkyl thienyl thienoindole thereof and photovoltaic device using same
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