KR20140018345A

KR20140018345A - Semiconductor materials based on dithienopyridone copolymers

Info

Publication number: KR20140018345A
Application number: KR1020137031041A
Authority: KR
Inventors: 아쇽 쿠마르 미쉬라; 수브라마니안 바이드야나탄; 히로요시 노구치; 플로리안 되츠; 유추이 구안
Original assignee: 바스프 에스이
Priority date: 2011-04-27
Filing date: 2012-04-16
Publication date: 2014-02-12
Also published as: KR101486693B1; WO2012146504A1; CN103517936A; JP2014518904A; EP2702085A1

Abstract

본 발명은 하기 화학식 1 및/또는 화학식 1'의 단위를 포함하는 중합체를 제공한다. 본 발명은 또한, 반도체 물질로서 상기 중합체를 포함하는 전자 소자를 제공한다.
<화학식 1>

<화학식 1'>

The present invention provides a polymer comprising units of the following general formula (1) and / or general formula (1 '). The present invention also provides an electronic device comprising the polymer as a semiconductor material.
&Lt; Formula 1 >

&Lt; Formula (1) >

Description

TECHNICAL FIELD [0001] The present invention relates to a semiconductor material based on dithienopyridone copolymers,

유기 반도체 물질은 전자 소자, 예컨대 유기 광기전 소자 (OPV), 유기 전계-효과 트랜지스터 (OFET), 유기 발광 다이오드 (OLED), 및 유기 전기변색 소자 (ECD)에 사용될 수 있다.Organic semiconductor materials can be used in electronic devices such as organic photovoltaic devices (OPV), organic field effect transistors (OFET), organic light emitting diodes (OLED), and organic electrochromic devices (ECD).

효율적이고 오래 지속되는 성능을 위해서는, 유기 반도체 물질 기재의 소자가 높은 전하 캐리어 이동도 뿐만 아니라, 주위 환경 조건 하에, 특히 공기에 의한 산화에 대해 높은 안정성을 나타내는 것이 바람직하다.For efficient and long lasting performance, it is desirable that devices based on organic semiconducting materials exhibit high stability against oxidation by air, especially under ambient environmental conditions, as well as high charge carrier mobility.

또한, 액체 가공 기술이 가공성의 관점에서 편리하기 때문에, 유기 반도체 물질이 액체 가공 기술, 예컨대 스핀 코팅과 상용성이고, 따라서 저비용 유기 반도체 물질 기재의 전자 소자의 제조를 가능하게 하는 것이 바람직하다. 추가로, 액체 가공 기술은 또한 플라스틱 기판과 상용성이고, 따라서 경량이고 기계적으로 유연한 유기 반도체 물질 기재의 전자 소자의 제조를 가능하게 한다.Further, since the liquid processing technique is convenient from the viewpoint of processability, it is desirable that the organic semiconductor material is compatible with liquid processing techniques such as spin coating, thus enabling the production of electronic devices based on low cost organic semiconductor materials. In addition, liquid processing techniques are also compatible with plastic substrates and thus enable the production of electronic devices based on lightweight, mechanically flexible organic semiconductor materials.

전자 소자에서의 중합체 유기 반도체 물질의 사용은 당업계에 공지되어 있다.The use of polymeric organic semiconductor materials in electronic devices is well known in the art.

문헌 [Zhang, M.; Tsao, H. N.; Pisula, W.; Yang, C.; Mishra, A. K.; Muellen, K. J. Am. Chem. Soc. 2007, 129, 3472-3473]에는 유기 전계 효과 트랜지스터 (OFET)에 사용하기 위한 하기 화학식의 중합체가 기재되어 있다.Zhang, M .; Tsao, H. N .; Pisula, W .; Yang, C .; Mishra, A. K .; Muellen, K. J. Am. Chem. Soc. 2007, 129, 3472-3473 describes polymers of the following formula for use in organic field effect transistors (OFET).

문헌 [Xiao, S; Zhou H.; You, W. Macromolecules 2008, 41, 5688-5696]에는 광기전 소자에 사용하기 위한 공여체 물질로서의 하기 중합체가 기재되어 있다.Xiao, S; Zhou H .; You, W. Macromolecules 2008, 41, 5688-5696, describes the following polymers as donor materials for use in photovoltaic devices.

문헌 [Scharber, M. C.; Koppe, M.; Gao, J.; Cordella, F.; Loi, M. A.; Denk, P.; Morana, M.; Egelhaaf, H.-J.; Forberich, K.; Dennler, G.; Gaudiana, R.; Waller, D.; Zhu, Z.; Shi, X.; Brabec, C. J. Adv. Mater. 2009, 21, 1-4]에는 태양 전지에 사용하기 위한 공여체 물질로서의 하기 중합체가 기재되어 있다.Scharber, M. C .; Koppe, M .; Gao, J .; Cordella, F .; Loi, M. A .; Denk, P .; Morana, M .; Egelhaaf, H. -J .; Forberich, K .; Dennler, G .; Gaudiana, R .; Waller, D .; Zhu, Z .; Shi, X .; Brabec, C. J. Adv. Mater. 2009, 21, 1-4] describes the following polymers as donor materials for use in solar cells.

문헌 [Rieger, R.; Beckmann, D.; Pisula, W.; Steffen, W.; Kastler, M.; Muellen K. Adv. Mater. 2010, 22, 83-86]에는 유기 전계-효과 트랜지스터 (OFET)에 사용하기 위한 하기 중합체가 기재되어 있다.Rieger, R .; Beckmann, D .; Pisula, W .; Steffen, W .; Kastler, M .; Muellen K. Adv. Mater. 2010, 22, 83-86, describes the following polymers for use in organic field-effect transistors (OFET).

문헌 [Junying Liu, Rui Zhang, Genevieve Sauve, Tomasz Kowalewski, Richard D. McCullough, J. Am. Chem. Soc. 2008, 130, 13167-13176]에는 유기 전계-효과 트랜지스터 (OFET)에 사용하기 위한 중합체가 기재되어 있다.Junying Liu, Rui Zhang, Genevieve Sauve, Tomasz Kowalewski, Richard D. McCullough, J. Am. Chem. Soc. 2008, 130, 13167-13176 describes polymers for use in organic field-effect transistors (OFET).

문헌 [Xugang Guo, Rocio P. Ortiz, Yan Zheng, Yan Hu, Yong-Young Noh, Kang-Jun Baeg, Antonio Facchetti, Tobin J. Marks, J. Am. Chem. Soc. 2011, 133, 1405-1418]에는 유기 전계-효과 트랜지스터 (OFET)에 사용하기 위한 중합체가 기재되어 있다.Kang-Jun Baeg, Antonio Facchetti, Tobin J. Marks, J. Am. Chem. Soc. 2011, 133, 1405-1418 describes polymers for use in organic field-effect transistors (OFET).

단량체 디티에노피리돈 또한 당업계에 공지되어 있다.Monomers dithienopyridones are also known in the art.

문헌 [G. J. Heeres and H. Wynberg, Synth. Comm. 1971, 1, 29 내지 31]에는 하기 화학식의 디티에노피리돈 단량체의 합성이 보고되어 있다.G. J. Heeres and H. Wynberg, Synth. Comm. 1971, 1, 29 to 31], the synthesis of dithienopyridone monomers of the following formula is reported.

본 발명의 목적은 신규 중합체 반도체 물질을 제공하는 것이었다.An object of the present invention was to provide a novel polymer semiconductor material.

상기 목적은 특허청구범위의 청구항 1의 중합체 및 청구항 15의 전자 소자에 의해 해결된다.This object is solved by the polymer of claim 1 of claim 1 and the electronic device of claim 15.

본 발명의 반도체 물질은 하기 화학식 1 및/또는 화학식 1'의 단위를 포함하는 중합체이다.The semiconductor material of the present invention is a polymer comprising units of the following general formula (1) and / or general formula (1 ').

<화학식 1>&Lt; Formula 1 >

<화학식 1'>&Lt; Formula (1) >

상기 식에서,Where

R¹은 H, 1 내지 6개의 치환기 R^c로 임의로 치환된 C₁ _-30-알킬, 1 내지 6개의 치환기 R^c로 임의로 치환된 C₂ _-30-알케닐, 1 내지 6개의 치환기 R^c로 임의로 치환된 C_2-30-알키닐, 1 내지 6개의 치환기 R^d로 임의로 치환된 C₃ _-10-시클로알킬, 1 내지 6개의 치환기 R^d로 임의로 치환된 C₅ _-10-시클로알케닐, 1 내지 6개의 치환기 R^d로 임의로 치환된 1가 3 내지 14원 지방족 헤테로시클릭 잔기, 1 내지 6개의 치환기 R^e로 임의로 치환된 C₆ _-14-아릴 또는 1 내지 6개의 치환기 R^e로 임의로 치환된 1가 5 내지 14원 방향족 헤테로시클릭 잔기이고, 여기서R ¹ is H, 1-6 substituents R ^c optionally substituted with C ₁ _{-30-a-alkenyl,} 1-6 substituents R ^c - alkyl, one to six substituents R ^c optionally substituted C ₂ to _-30 optionally substituted C _2-30 - alkynyl, 1-6 substituents R ^d, optionally substituted C ₃ _-10 by-cycloalkyl, 1-6 substituents R ^d optionally substituted with C ₅ _{-10-cycloalkenyl,} optionally substituted with aryl, or 1-6 substituents R ^e - 1 to 6 substituents R ^d with an optionally substituted 1, 3 to 14-membered aliphatic heterocyclic moiety, 1 to 6 in the substituent R ^e is optionally substituted C ₆ _-14 Substituted monovalent 5- to 14-membered aromatic heterocyclic moiety, wherein

R^c는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR², -S-C₁ _-10-알킬, -NH₂, -NHR², -NR²R³, -NH-COR², -COOH, -COOR², -CONH₂, -CONHR², -CONR²R³, -CO-H, -COR², C_3-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ^c is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-10 -alkyl, -O-COR ² , -SC ₁ _-10 -alkyl, -NH ₂ , -NHR ² , -NR ² R ³ , -NH-COR ² , -COOH , -COOR ² , -CONH ₂ , -CONHR ² , -CONR ² R ³ , -CO-H, -COR ² , C _3-10 -cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic moiety, C ₆ _-14 -aryl and _{monovalent 5-14} membered aromatic heterocyclic moiety;

R^d는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR², -S-C₁ _-10-알킬, -NH₂, -NHR², -NR²R³, -NH-COR², -COOH, -COOR², -CONH₂, -CONHR², -CONR²R³, -CO-H, -COR², C_1-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ^d is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , _-14 C ₆ - is selected from aryl, and the group 1 is made of a 5- to 14-membered aromatic heterocyclic residue,

R^e는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR², -S-C₁ _-10-알킬, -NH₂, -NHR², -NR²R³, -NH-COR², -COOH, -COOR², -CONH₂, -CONHR², -CONR²R³, -CO-H, -COR², C_1-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐 및 1가 3 내지 14원 지방족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^e is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residues, wherein

R² 및 R³은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C_3-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ² and R ³ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C _3-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

X는 N 또는 C-R⁴이고, 여기서X is N or CR < ⁴ >, wherein

R⁴는 H, 1 내지 6개의 치환기 R^f로 임의로 치환된 C₁ _-30-알킬, 1 내지 6개의 치환기 R^f로 임의로 치환된 C₂ _-30-알케닐, 1 내지 6개의 치환기 R^f로 임의로 치환된 C_2-30-알키닐, 1 내지 6개의 치환기 R^g로 임의로 치환된 C₃ _-10-시클로알킬, 1 내지 6개의 치환기 R^g로 임의로 치환된 C₅ _-10-시클로알케닐, 1 내지 6개의 치환기 R^g로 임의로 치환된 1가 3 내지 14원 지방족 헤테로시클릭 잔기, 1 내지 6개의 치환기 R^h로 임의로 치환된 C₆ _-14-아릴 또는 1 내지 6개의 치환기 R^h로 임의로 치환된 1가 5 내지 14원 방향족 헤테로시클릭 잔기이고, 여기서R ⁴ is H, 1 to 6 substituents R ^f optionally substituted with C ₁ _-30-alkyl, one to six substituents R ^f as an optionally substituted C ₂ _{-30-to-alkenyl,} of one to six substituents R ^f optionally substituted C _2-30 - alkynyl, 1-6 substituents R ^g optionally substituted C ₃ _-10 by-cycloalkyl, 1-6 substituents R ^g optionally substituted with C ₅ _{-10-cycloalkenyl,} 1 to 6 substituents R ^g as optionally substituted monovalent aliphatic 3-to 14-membered heterocyclic residue with 1 to 6 substituents R ^h, optionally substituted C ₆ _-14 a-aryl, or 1-6 substituents R ^h, optionally Substituted monovalent 5- to 14-membered aromatic heterocyclic moiety, wherein

R^f는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR⁵, -S-C₁ _-10-알킬, -NH₂, -NHR⁵, -NR⁵R⁶, -NH-COR⁵, -COOH, -COOR⁵, -CONH₂, -CONHR⁵, -CONR⁵R⁶, -CO-H, -COR⁵, C_3-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ^f is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,

R^g는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR⁵, -S-C₁ _-10-알킬, -NH₂, -NHR⁵, -NR⁵R⁶, -NH-COR⁵, -COOH, -COOR⁵, -CONH₂, -CONHR⁵, -CONR⁵R⁶, -CO-H, -COR⁵, C_1-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ^g is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , _-14 C ₆ - is selected from aryl, and the group 1 is made of a 5- to 14-membered aromatic heterocyclic residue,

R^h는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR⁵, -S-C₁ _-10-알킬, -NH₂, -NHR⁵, -NR⁵R⁶, -NH-COR⁵, -COOH, -COOR⁵, -CONH₂, -CONHR⁵, -CONR⁵R⁶, -CO-H, -COR⁵, C_1-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐 및 1가 3 내지 14원 지방족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^h is independently from each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residues, wherein

R⁵ 및 R⁶은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl C _1-6 -alkenyl, monovalent 3- to 14-membered aliphatic heterocyclic moieties, C _6-14 -aryl and monovalent 5- to 14-membered aromatic heterocyclic residues,

G¹ 및 G²는 서로 독립적으로 1 내지 6개의 치환기 R^a로 임의로 치환된 C₆ _-14-아릴렌 또는 1 내지 6개의 치환기 R^a로 임의로 치환된 2가 5 내지 14원 방향족 헤테로시클릭 잔기이고, 여기서G ¹ and G ² are independently of one to six substituents R ^a as an optionally substituted C ₆ _-14 each other arylene or 1-6 substituents R ^a as an optionally substituted divalent 5-to 14-membered aromatic heterocyclic residue , Where

R^a는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-30-알콕시, -O-CH₂CH₂O-C₁ _-30-알킬, -O-COR⁸, -S-C₁ _-30-알킬, -NH₂, -NHR⁸, -NR⁸R⁹, -NH-COR⁸, -COOH, -COOR⁸, -CONH₂, -CONHR⁸, -CONR⁸R⁹, -CO-H, -COR⁸, 1 내지 6개의 치환기 Rⁱ로 임의로 치환된 C₁ _-30-알킬, 1 내지 6개의 치환기 Rⁱ로 임의로 치환된 C₂ _-30-알케닐, 1 내지 6개의 치환기 Rⁱ로 임의로 치환된 C₂ _-30-알키닐, 1 내지 6개의 치환기 R^j로 임의로 치환된 C₃ _-10-시클로알킬, 1 내지 6개의 치환기 R^j로 임의로 치환된 C₅ _-10-시클로알케닐 및 1 내지 6개의 치환기 R^j로 임의로 치환된 1가 3 내지 14원 지방족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^a is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -30 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-30 -alkyl, -O-COR ⁸ , -SC ₁ _-30 -alkyl, -NH ₂ , -NHR ⁸ , -NR ⁸ R ⁹ , -NH-COR ⁸ , -COOH , -COOR ⁸ , -CONH ₂ , -CONHR ⁸ , -CONR ⁸ R ⁹ , -CO-H, -COR ⁸ , C ₁ _-30 -alkyl optionally substituted with 1 to 6 substituents R ⁱ , the substituent optionally substituted with R ⁱ C ₂ _-30-alkenyl, one to six substituents R ^i, form a C ₂ _{-30-substituted-alkynyl,} one to six substituents R ^j optionally substituted C ₃ _-10 - selected from cycloalkenyl and 1-6 substituents group is optionally substituted by 1 R ^j consisting of a 3 to 14-membered aliphatic heterocyclic residue-cycloalkyl, 1-6 substituents R ^j optionally substituted C ₅ _-10 to , Where

R⁸ 및 R⁹는 각 경우에 서로 독립적으로 C₁ _-30-알킬, C₂ _-30-알케닐, C₂ _-30-알키닐, C_3-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁸ and R ⁹ in each case independently of _one another are C ₁ _-30 -alkyl, C ₂ _-30 -alkenyl, C ₂ _-30 -alkynyl, C _3-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

Rⁱ는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR¹⁰, -S-C₁ _-10-알킬, -NH₂, -NHR¹⁰, -NR¹⁰R¹¹, -NH-COR¹⁰, -COOH, -COOR¹⁰, -CONH₂, -CONHR¹⁰, -CONR¹⁰R¹¹, -CO-H, -COR¹⁰, C₃ _-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁱ is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 10, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 10, -NR}} 10 R 11, -NH-COR 10, -COOH ^{_{, -COOR 10, -CONH 2, -CONHR}} 10, -CONR 10 R 11, -CO-H, -COR 10, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,

R^j는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR¹⁰, -S-C₁ _-10-알킬, -NH₂, -NHR¹⁰, -NR¹⁰R¹¹, -NH-COR¹⁰, -COOH, -COOR¹⁰, -CONH₂, -CONHR¹⁰, -CONR¹⁰R¹¹, -CO-H, -COR¹⁰, C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^j is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 10, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 10, -NR}} 10 R 11, -NH-COR 10, -COOH ^{_{, -COOR 10, -CONH 2, -CONHR}} 10, -CONR 10 R 11, -CO-H, -COR 10, C 1 -10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein

R¹⁰ 및 R¹¹은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C_2-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되거나,R ¹⁰ and R ¹¹ are each independently at each occurrence C ₁ _-10 - alkyl, C ₂ _-10 - alkenyl, C _2-10 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - or selected from the group consisting of aryl and 1 is 5 to 14-membered aromatic heterocyclic residue,

또는or

G¹ 및 G²는 서로 독립적으로G ¹ and G ² are independently of each other

이고, 여기서, Where

R¹⁸ 및 R¹⁹는 서로 독립적으로 H 또는 C₁ _-30-알킬이고,Alkyl, - R ¹⁸ and R ¹⁹ are independently H or C ₁ _-30 from each other

L은 1 내지 6개의 치환기 R^b로 임의로 치환된 C₆ _-24-아릴렌 또는 1 내지 6개의 치환기 R^b로 임의로 치환된 2가 5 내지 24원 방향족 헤테로시클릭 잔기이고, 여기서L is a divalent 5- to 24-membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R ^b , optionally substituted with C ₆ _-24 -arylene or 1 to 6 substituents R ^b , wherein

R^b는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-30-알콕시, -O-CH₂CH₂O-C₁ _-30-알킬, -O-COR¹², -S-C₁ _-30-알킬, -NH₂, -NHR¹², -NR¹²R¹³, -NH-COR¹², -COOH, -COOR¹², -CONH₂, -CONHR¹², -CONR¹²R¹³, -CO-H, -COR¹², 1 내지 6개의 치환기 R^k로 임의로 치환된 C₁ _-30-알킬, 1 내지 6개의 치환기 R^k로 임의로 치환된 C₂ _-30-알케닐, 1 내지 6개의 치환기 R^k로 임의로 치환된 C₂ _-30-알키닐, 1 내지 6개의 치환기 R^l로 임의로 치환된 C₃ _-10-시클로알킬, 1 내지 6개의 치환기 R^l로 임의로 치환된 C₅ _-10-시클로알케닐 및 1 내지 6개의 치환기 R^l로 임의로 치환된 1가 3 내지 14원 지방족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^b is independently from each other in each case = _{O, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -30 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-30 -alkyl, -O-COR ¹² , -SC ₁ _-30 -alkyl, -NH ₂ , -NHR ¹² , -NR ¹² R ¹³ , -NH-COR ¹² , -COOH , -COOR ¹² , -CONH ₂ , -CONHR ¹² , -CONR ¹² R ¹³ , -CO-H, -COR ¹² , C ₁ _-30 -alkyl optionally substituted with 1 to 6 substituents R ^k , the substituent optionally substituted with R ^k C ₂ _-30 - alkenyl with 1 to 6 substituents R ^k optionally substituted C ₂ _-30 - alkynyl, 1-6 substituents R ^l optionally substituted with C ₃ _-10 - selected from cycloalkenyl and 1-6 substituents R ^l group consisting of optionally substituted 1 is a 3 to 14 membered aliphatic heterocyclic residue as - cycloalkyl, 1-6 substituents R ^l, optionally substituted C ₅ _-10 to , Where

R¹² 및 R¹³은 각 경우에 서로 독립적으로 C₁ _-30-알킬, C₂ _-30-알케닐, C₂ _-30-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ¹² and R ¹³ are each independently at each occurrence C ₁ _-30 - alkyl, C ₂ _-30 - alkenyl, C ₂ _-30 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl C _1-6 -alkenyl, monovalent 3- to 14-membered aliphatic heterocyclic moieties, C _6-14 -aryl and monovalent 5- to 14-membered aromatic heterocyclic residues,

R^k는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR¹⁴, -S-C₁ _-10-알킬, -NH₂, -NHR¹⁴, -NR¹⁴R¹⁵, -NH-COR¹⁴, -COOH, -COOR¹⁴, -CONH₂, -CONHR¹⁴, -CONR¹⁴R¹⁵, -CO-H, -COR¹⁴, C₃ _-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ^k is independently = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 14, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 14, -NR}} 14 R 15, -NH-COR 14, -COOH ^{_{, -COOR 14, -CONH 2, -CONHR}} 14, -CONR 14 R 15, -CO-H, -COR 14, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,

R^l은 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR¹⁴, -S-C₁ _-10-알킬, -NH₂, -NHR¹⁴, -NR¹⁴R¹⁵, -NH-COR¹⁴, -COOH, -COOR¹⁴, -CONH₂, -CONHR¹⁴, -CONR¹⁴R¹⁵, -CO-H, -COR¹⁴, C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^l is independently from each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 14, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 14, -NR}} 14 R 15, -NH-COR 14, -COOH ^{_{, -COOR 14, -CONH 2, -CONHR}} 14, -CONR 14 R 15, -CO-H, -COR 14, C 1 -10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein

R¹⁴ 및 R¹⁵는 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C_2-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되거나,R ¹⁴ and R ¹⁵ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - or selected from the group consisting of aryl and 1 is 5 to 14-membered aromatic heterocyclic residue,

또는or

L은L is

이고, 여기서, Where

R¹⁶ 및 R¹⁷은 서로 독립적으로 H, C₁ _-30-알킬, -CN 또는 할로겐이고,R ¹⁶ and R ^17, independently of each other H, C ₁ _-30 - alkyl, -CN or halogen,

q 및 s는 서로 독립적으로 0, 1, 2, 3, 4 또는 5이고,q and s are independently of each other 0, 1, 2, 3, 4 or 5,

r은 0, 1 또는 2이고, r is 0, 1 or 2,

n은 2 내지 10,000의 정수이다.and n is an integer of 2 to 10,000.

바람직하게는, 본 발명의 반도체 물질은 본질적으로 하기 화학식 1의 단위 및/또는 하기 화학식 1'의 단위로 이루어진 중합체이다.Preferably, the semiconductor material of the present invention is a polymer consisting essentially of units of the formula (1) and / or units of the formula (1 '):

<화학식 1>&Lt; Formula 1 >

<화학식 1'>&Lt; Formula (1) >

상기 식에서,Where

R² 및 R³은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C_3-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ² and R ³ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C _3-10 -cycloalkyl, C ₅ _-10 -cycloalkyl C _1-6 -alkenyl, monovalent 3- to 14-membered aliphatic heterocyclic moieties, C _6-14 -aryl and monovalent 5- to 14-membered aromatic heterocyclic residues,

X는 N 또는 C-R⁴이고, 여기서X is N or CR < ⁴ >, wherein

R⁵ 및 R⁶은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

R⁸ 및 R⁹는 각 경우에 서로 독립적으로 C₁ _-30-알킬, C₂ _-30-알케닐, C_2-30-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁸ and R ⁹ in each case independently of _one another are C ₁ _-30 -alkyl, C ₂ _-30 -alkenyl, C _2-30 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

또는or

이고, 여기서, Where

또는or

L은L is

이고, 여기서, Where

r은 0, 1 또는 2이고, r is 0, 1 or 2,

n은 2 내지 10,000의 정수이다.and n is an integer of 2 to 10,000.

용어 "본질적으로 이루어진"은, 중합체의 중량을 기준으로 하여, 중합체의 80 중량% 이상, 보다 바람직하게는 90 중량% 이상이 화학식 1 및 1'의 단위 합계로 이루어진 것을 의미한다.The term "consisting essentially of " means that at least 80 wt%, more preferably at least 90 wt% of the polymer is composed of the sum of units of formulas (1) and (1 '), based on the weight of the polymer.

보다 바람직하게는, 본 발명의 반도체 물질은 하기 화학식 1의 단위 또는 하기 화학식 1'의 단위로 이루어진 중합체이다.More preferably, the semiconductor material of the present invention is a polymer comprising units of the following formula (1) or units of the following formula (1 ').

<화학식 1>&Lt; Formula 1 >

<화학식 1'>&Lt; Formula (1) >

상기 식에서,Where

R² 및 R³은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C_2-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ² and R ³ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

X는 N 또는 C-R⁴이고, 여기서X is N or CR < ⁴ >, wherein

또는or

이고, 여기서, Where

또는or

L은L is

이고, 여기서, Where

r은 0, 1 또는 2이고, r is 0, 1 or 2,

n은 2 내지 10,000의 정수이다.and n is an integer of 2 to 10,000.

C₁ _-10-알킬 및 C₁ _-30-알킬은 분지형 또는 비분지형일 수 있다. C₁ _-10-알킬의 예는 메틸, 에틸, n-프로필, 이소프로필, n-부틸, sec-부틸, 이소부틸, tert-부틸, n-펜틸, 네오펜틸, 이소펜틸, n-(1-에틸)프로필, n-헥실, n-헵틸, n-옥틸, n-(2-에틸)헥실, n-노닐 및 n-데실이다. C₁ _-30-알킬의 예는 C₁ _-10-알킬, 및 n-운데실, n-도데실, n-운데실, n-도데실, n-트리데실, n-테트라데실, n-펜타데실, n-헥사데실, n-헵타데실, n-옥타데실, n-노나데실 및 n-이코실 (C₂₀), n-도코실 (C₂₂), n-테트라코실 (C₂₄), n-헥사코실 (C₂₆), n-옥타코실 (C₂₈) 및 n-트리아콘틸 (C₃₀)이다. C ₁ _-10 -alkyl and C ₁ _-30 -alkyl may be branched or unbranched. Examples of C ₁ _-10 -alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, n- pentyl, neopentyl, Ethyl) propyl, n-hexyl, n-heptyl, n-octyl, n- (2-ethyl) hexyl, n-nonyl and n-decyl. Examples of C ₁ _-30 -alkyl are C ₁ _-10 -alkyl, and n-pentyl, n-octyl, n-decyl, n-undecyl, n-dodecyl, decyl, n- hexadecyl, n- heptadecyl, n- octadecyl, n- nonadecyl and n- Ikoma chamber ₍₂₀ C), n- docosyl (C _22), n- tetracosyl (C _24), n -Hexacosyl (C ₂₆ ), n-octacosyl (C ₂₈ ) and n-triacontyl (C ₃₀ ).

C₂ _-10-알케닐 및 C₂ _-30-알케닐은 분지형 또는 비분지형일 수 있다. C₂ _-10-알케닐의 예는 비닐, 프로페닐, 시스-2-부테닐, 트랜스-2-부테닐, 3-부테닐, 시스-2-펜테닐, 트랜스-2-펜테닐, 시스-3-펜테닐, 트랜스-3-펜테닐, 4-펜테닐, 2-메틸-3-부테닐, 헥세닐, 헵테닐, 옥테닐, 노네닐 및 도세닐이다. C₂ _-30-알케닐의 예는 C₂ _-10-알케닐, 및 리놀레일 (C₁₈), 리놀레닐 (C₁₈), 올레일 (C₁₈), 아라키도닐 (C₂₀), 및 에루실 (C₂₂)이다.C ₂ _-10 -alkenyl and C ₂ _-30 -alkenyl may be branched or unbranched. Examples of C ₂ _-10 -alkenyl are vinyl, propenyl, cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis- Pentenyl, trans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl. C ₂ _-30 - Examples of alkenyl is C ₂ _-10 - alkenyl, and linoleyl (C _18), linoleic alkylenyl (C _18), oleyl (C _18), Araki FIG carbonyl (C _20), and the Lucil (C ₂₂ ).

C₂ _-10-알키닐 및 C₂ _-30-알키닐은 분지형 또는 비분지형일 수 있다. C₂ _-10-알키닐의 예는 에티닐, 2-프로피닐, 2-부티닐, 3-부티닐, 펜티닐, 헥시닐, 헵티닐, 옥티닐, 노니닐 및 데시닐이다. C₂ _-30-알키닐의 예는 C₂ _-10-알키닐, 및 운데시닐, 도데시닐, 운데시닐, 도데시닐, 트리데시닐, 테트라데시닐, 펜타데시닐, 헥사데시닐, 헵타데시닐, 옥타데시닐, 노나데시닐 및 이코시닐 (C₂₀)이다.C ₂ _-10 - alkynyl, and C ₂ _-30 - alkynyl may be branched or unbranched. Examples of C ₂ _-10 -alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl. Examples of C ₂ _-30 -alkynyl include C ₂ _-10 -alkynyl, and undecyl, undecyl, undecyl, dodecyl, tridecyl, tetradecynyl, pentadecynyl, hexadecynyl , Heptadecynyl, octadecynyl, nonadecynyl, and eicosinyl (C ₂₀ ).

C₃ _-10-시클로알킬의 예는 바람직하게는 모노시클릭 C₃ _-10-시클로알킬, 예컨대 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실, 시클로헵틸 및 시클로옥틸이지만, 또한 폴리시클릭 C₃ _-10-시클로알킬, 예컨대 데칼리닐, 노르보르닐 및 아다만틸도 포함한다.Examples of C ₃ _-10 -cycloalkyl are preferably monocyclic C ₃ _-10 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but also polycyclic C ₃ _{- 10} -cycloalkyl, such as decalinyl, norbornyl and adamantyl.

C₅ _-10-시클로알케닐의 예는 바람직하게는 모노시클릭 C₅ _-10-시클로알케닐, 예컨대 시클로펜테닐, 시클로헥세닐, 시클로헥사디에닐 및 시클로헵타트리에닐이지만, 또한 폴리시클릭 C₅ _-10-시클로알케닐도 포함한다.Examples of C ₅ _-10 -cycloalkenyl are preferably monocyclic C ₅ _-10 -cycloalkenyl such as cyclopentenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but also polycyclic C ₅ _-10 -cycloalkenyl.

1가 3 내지 14원 지방족 헤테로시클릭 잔기의 예는 모노시클릭 1가 3 내지 8원 지방족 시클릭 잔기 및 폴리시클릭, 예를 들어 비시클릭 1가 7 내지 12원 지방족 헤테로시클릭 잔기이다.Examples of monovalent 3- to 14-membered aliphatic heterocyclic moieties are monocyclic monovalent 3- to 8-membered aliphatic cyclic moieties and polycyclic, such as bicyclic 1, 7 to 12 membered aliphatic heterocyclic moieties.

모노시클릭 1가 3 내지 8원 지방족 헤테로시클릭 잔기의 예는 1개의 헤테로원자를 함유하는 모노시클릭 1가 5원 지방족 헤테로시클릭 잔기, 예컨대 피롤리디닐, 1-피롤리닐, 2-피롤리닐, 3-피롤리닐, 테트라히드로푸릴, 2,3-디히드로푸릴, 테트라히드로티오페닐 및 2,3-디히드로티오페닐, 2개의 헤테로원자를 함유하는 모노시클릭 1가 5원 지방족 헤테로시클릭 잔기, 예컨대 이미다졸리디닐, 이미다졸리닐, 피라졸리디닐, 피라졸리닐, 옥사졸리디닐, 옥사졸리닐, 이속사졸리디닐, 이속사졸리닐, 티아졸리디닐, 티아졸리닐, 이소티아졸리디닐 및 이소티아졸리닐, 3개의 헤테로원자를 함유하는 모노시클릭 1가 5원 지방족 헤테로시클릭 잔기, 예컨대 1,2,3-트리아졸릴, 1,2,4-트리아졸릴 및 1,4,2-디티아졸릴, 1개의 헤테로원자를 함유하는 모노시클릭 1가 6원 지방족 헤테로시클릭 잔기, 예컨대 피페리딜, 피페리디노, 테트라히드로피라닐, 피라닐, 티아닐 및 티오피라닐, 2개의 헤테로원자를 함유하는 모노시클릭 1가 6원 지방족 헤테로시클릭 잔기, 예컨대 피페라지닐, 모르폴리닐 및 모르폴리노 및 티아지닐, 1개의 헤테로원자를 함유하는 모노시클릭 1가 7원 지방족 헤테로시클릭 잔기, 예컨대 아제파닐, 아제피닐, 옥세파닐, 티에파닐, 티아파닐, 티에피닐, 및 2개의 헤테로원자를 함유하는 모노시클릭 1가 7원 지방족 헤테로시클릭 잔기, 예컨대 1,2-디아제피닐 및 1,3-티아제피닐이다.Examples of monocyclic monovalent 3-8 membered aliphatic heterocyclic residues are monocyclic monovalent 5-membered aliphatic heterocyclic residues containing one heteroatom such as pyrrolidinyl, 1-pyrrolinyl, 2- Pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and 2,3-dihydrothiophenyl, monocyclic monovalent 5-membered containing two heteroatoms Aliphatic heterocyclic moieties such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thiazolinyl Isothiazolidinyl and isothiazolinyl, monocyclic monovalent 5-membered aliphatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazolyl, 1,2,4-triazolyl and 1,4,2-dithiazolyl, monocyclic monovalent 6-membered aliphatic hex containing one heteroatom Teroxycyclic moieties such as piperidyl, piperidino, tetrahydropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic monovalent 6-membered aliphatic heterocyclic moieties containing two heteroatoms such as Piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic monovalent 7-membered aliphatic heterocyclic moieties containing one heteroatom such as azepanyl, azepinyl, oxepanyl, thiepanyl, Monocyclic monovalent seven-membered aliphatic heterocyclic moieties containing thiaphanyl, thiepynyl, and two heteroatoms such as 1,2-diazepinyl and 1,3-thiazepinyl.

비시클릭 1가 7 내지 12원 지방족 헤테로시클릭 잔기의 일례는 데카히드로나프틸이다.An example of a bicyclic monovalent 7 to 12 membered aliphatic heterocyclic residue is decahydronaphthyl.

C₆ _-14-아릴은 모노시클릭 또는 폴리시클릭일 수 있다. C₆ _-14-아릴의 예는 모노시클릭 C₆-아릴, 예컨대 페닐, 비시클릭 C₉ _-10-아릴, 예컨대 1-나프틸, 2-나프틸, 인데닐, 인다닐 및 테트라히드로나프틸, 및 트리시클릭 C₁₂ _-14-아릴, 예컨대 안트릴, 페난트릴, 플루오레닐 및 s-인다세닐이다.C ₆ _-14 - aryl may be monocyclic or polycyclic. Examples of C ₆ _-14 -aryl are monocyclic C ₆ -aryl, such as phenyl, bicyclic C ₉ _-10 -aryl, such as 1-naphthyl, 2-naphthyl, indenyl, indanyl and tetrahydronaphthyl , And tricyclic C ₁₂ _-14 -aryl, such as anthryl, phenanthryl, fluorenyl, and s-indacenyl.

1가 5 내지 14원 방향족 헤테로시클릭 잔기는 모노시클릭 1가 5 내지 8원 방향족 헤테로시클릭 잔기, 또는 폴리시클릭, 예를 들어 비시클릭 1가 7 내지 12원, 트리시클릭 1가 9 내지 14원 방향족 헤테로시클릭 잔기, 또는 테트라시클릭 1가 9 내지 14원 방향족 헤테로시클릭 잔기일 수 있다.Monovalent 5- to 14-membered aromatic heterocyclic residues may be monocyclic monovalent 5- to 8-membered aromatic heterocyclic residues, or polycyclic, such as bicyclic 1 is 7-12 membered, tricyclic 1 is 9-14 Membered aromatic heterocyclic residue, or tetracyclic 1 may be a 9 to 14 membered aromatic heterocyclic residue.

모노시클릭 1가 5 내지 8원 방향족 헤테로시클릭 잔기의 예는 1개의 헤테로원자를 함유하는 모노시클릭 1가 5원 방향족 헤테로시클릭 잔기, 예컨대 피롤릴, 푸릴 및 티오페닐, 2개의 헤테로원자를 함유하는 모노시클릭 1가 5원 방향족 헤테로시클릭 잔기, 예컨대 이미다졸릴, 피라졸릴, 옥사졸릴, 이속사졸릴, 티아졸릴, 이소티아졸릴, 3개의 헤테로원자를 함유하는 모노시클릭 1가 5원 방향족 헤테로시클릭 잔기, 예컨대 1,2,3-트리아졸릴, 1,2,4-트리아졸릴 및 옥사디아졸릴, 4개의 헤테로원자를 함유하는 모노시클릭 1가 5원 방향족 헤테로시클릭 잔기, 예컨대 테트라졸릴, 1개의 헤테로원자를 함유하는 모노시클릭 1가 6원 방향족 헤테로시클릭 잔기, 예컨대 피리딜, 2개의 헤테로원자를 함유하는 모노시클릭 1가 6원 방향족 헤테로시클릭 잔기, 예컨대 피라지닐, 피리미디닐 및 피리다지닐, 3개의 헤테로원자를 함유하는 모노시클릭 1가 6원 방향족 헤테로시클릭 잔기, 예컨대 1,2,3-트리아지닐, 1,2,4-트리아지닐 및 1,3,5-트리아지닐, 1개의 헤테로원자를 함유하는 모노시클릭 1가 7원 방향족 헤테로시클릭 잔기, 예컨대 아제피닐, 및 2개의 헤테로원자를 함유하는 모노시클릭 1가 7원 방향족 헤테로시클릭 잔기, 예컨대 1,2-디아제피닐이다.Examples of monocyclic monovalent 5- to 8-membered aromatic heterocyclic residues include monocyclic monovalent 5-membered aromatic heterocyclic residues containing one heteroatom, such as pyrrolyl, furyl and thiophenyl, two heteroatoms Monocyclic monovalent 5-membered aromatic heterocyclic moieties containing such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, monocyclic monovalent containing 3 heteroatoms 5-membered aromatic heterocyclic residues such as 1,2,3-triazolyl, 1,2,4-triazolyl and oxdiazolyl, monocyclic monovalent 5-membered aromatic heterocyclic residues containing four heteroatoms For example tetrazolyl, monocyclic monovalent six-membered aromatic heterocyclic residue containing one heteroatom such as pyridyl, monocyclic monovalent six-membered aromatic heterocyclic residue containing two heteroatoms such as Pyrazinyl , Pyrimidinyl and pyridazinyl, monocyclic monovalent 6-membered aromatic heterocyclic moieties containing three heteroatoms such as 1,2,3-triazinyl, 1,2,4-triazinyl and 1, 3,5-triazinyl, monocyclic monovalent 7-membered aromatic heterocyclic moiety containing 1 heteroatom such as azefinyl, and monocyclic monovalent 7-membered aromatic heterocyt containing 2 heteroatoms Click residues such as 1,2-diazefinyl.

비시클릭 1가 7 내지 12원 방향족 헤테로시클릭 잔기의 예는 2개의 헤테로원자를 함유하는 비시클릭 1가 8원 방향족 헤테로시클릭 잔기, 예컨대 티에노[3,2-b]티오페닐, 1개의 헤테로원자를 함유하는 비시클릭 9원 방향족 헤테로시클릭 잔기, 예컨대 인돌릴, 이소인돌릴, 인돌리지닐, 인돌리닐, 벤조푸릴, 이소벤조푸릴, 벤조티오페닐 및 이소벤조티오페닐, 2개의 헤테로원자를 함유하는 비시클릭 1가 9원 방향족 헤테로시클릭 잔기, 예컨대 인다졸릴, 벤즈이미다졸릴, 벤즈이미다졸리닐, 벤족사졸릴, 벤즈이소옥사졸릴, 벤즈티아졸릴, 벤즈이소티아졸릴, 푸로피리딜 및 티에노피리딜, 3개의 헤테로원자를 함유하는 비시클릭 1가 9원 방향족 헤테로시클릭 잔기, 예컨대 벤조트리아졸릴, 벤족사디아졸릴, 옥사졸로피리딜, 이소옥사졸로피리딜, 티아졸로피리딜, 이소티아졸로피리딜 및 이미다조피리딜, 4개의 헤테로원자를 함유하는 비시클릭 1가 9원 방향족 헤테로시클릭 잔기, 예컨대 퓨리닐, 1개의 헤테로원자를 함유하는 비시클릭 1가 10원 방향족 헤테로시클릭 잔기, 예컨대 퀴놀릴, 이소퀴놀릴, 크로메닐 및 크로마닐, 2개의 헤테로원자를 함유하는 비시클릭 1가 10원 방향족 헤테로시클릭 잔기, 예컨대 퀴녹살리닐, 퀴나졸리닐, 신놀리닐, 프탈라지닐, 1,5-나프티리디닐 및 1,8-나프티리디닐, 3개의 헤테로원자를 함유하는 비시클릭 1가 10원 방향족 헤테로시클릭 잔기, 예컨대 피리도피라지닐, 피리도피리미디닐 및 피리도피리다지닐, 및 4개의 헤테로원자를 함유하는 비시클릭 1가 10원 방향족 헤테로시클릭 잔기, 예컨대 프테리디닐이다.Examples of bicyclic monovalent 7 to 12 membered aromatic heterocyclic moieties include bicyclic monovalent 8-membered aromatic heterocyclic moieties containing two heteroatoms such as thieno [3,2-b] thiophenyl, one A bicyclic 9-membered aromatic heterocyclic residue containing a heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, benzothiophenyl and isobenzothiophenyl, two heteroatoms Is a 9-membered aromatic heterocyclic residue containing a bicyclic 1-membered aromatic heterocyclic residue containing 1 to 6 carbon atoms, such as indazolyl, benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzisothiazolyl, And thienopyridyl, bicyclic 1-substituted 9-membered aromatic heterocyclic residues containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isoxazolopyridyl, thiazolopyryl Dill, Thiazolopyridyl and imidazopyridyl, bicyclic 1-membered 9-membered aromatic heterocyclic moieties containing 4 heteroatoms such as furidinyl, bicyclic 1-membered aromatic heterocyclic rings containing 1 heteroatom A cyclic moiety such as quinolyl, isoquinolyl, chromenyl and chromanyl, a bicyclic 1-membered aromatic heterocyclic residue containing two heteroatoms such as quinoxalinyl, quinazolinyl, cinnolinyl, Thiazinyl, 1,5-naphthyridinyl and 1,8-naphthyridinyl, bicyclic 1-membered aromatic heterocyclic residues containing three heteroatoms, such as pyridopyrjinyl, pyridopyrimidinyl and pyridopyrimidinyl, Pyridopyridazinyl, and bicyclic 1-membered aromatic heterocyclic residues containing four heteroatoms, such as pteridinyl.

트리시클릭 1가 9 내지 14원 방향족 헤테로시클릭 잔기의 예는 디벤조푸릴, 아크리디닐, 페녹사지닐, 7H-시클로펜타[1,2-b:3,4-b']디티오페닐 및 4H-시클로펜타[2,1-b:3,4-b']디티오페닐이다. 3개의 헤테로원자를 함유하는 트리시클릭 1가 9 내지 14원 방향족 헤테로시클릭 잔기의 일례는 하기 화학식의 디티에노티오페닐이다.Examples of tricyclic monovalent 9-14 membered aromatic heterocyclic moieties include dibenzofuryl, acridinyl, phenoxazinyl, 7H-cyclopenta [1,2-b: 3,4-b '] dithiophenyl and 4H-cyclopenta [2,1-b: 3,4-b '] dithiophenyl. An example of a tricyclic monocyclic 9 to 14 membered aromatic heterocyclic residue containing three heteroatoms is dithienothiophenyl of the formula:

4개의 헤테로원자를 함유하는 테트라시클릭 1가 9 내지 14원 방향족 헤테로시클릭 잔기의 일례는 하기 화학식의 트리티에노티오페닐이다.An example of a tetracyclic monocyclic 9 to 14 membered aromatic heterocyclic residue containing four heteroatoms is tritynantiophenyl of the formula:

할로겐의 예는 -F, -Cl, -Br 및 -I이다.Examples of halogen are -F, -Cl, -Br and -I.

C₁ _-10-알콕시의 예는 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, sec-부톡시, 이소부톡시, tert-부톡시, n-펜톡시, 네오펜톡시, 이소펜톡시, 헥속시, n-헵톡시, n-옥톡시, n-노녹시 및 n-데콕시이다. C₁ _-30-알콕시의 예는 C₁ _-10-알콕시, 및 n-운데콕시, n-도데콕시, n-운데콕시, n-도데콕시, n-트리데콕시, n-테트라데콕시, n-펜타데콕시, n-헥사데콕시, n-헵타데콕시, n-옥타데콕시, n-노나데콕시 및 n-이코속시 (C₂₀), n-도코속시 (C₂₂), n-테트라코속시 (C₂₄), n-헥사코속시 (C₂₆), n-옥타코속시 (C₂₈) 및 n-트리아콘톡시 (C₃₀)이다.Examples of C ₁ _-10 -alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert- , Isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy. Examples of C ₁ _-30 -alkoxy include C ₁ _-10 -alkoxy, and n-butoxy, n-dodecoxy, n-undecoxy, n-dodecoxy, N-hexadecoxy, n-heptadecoxy, n-octadecoxy, n-nonadecoxy and n-icocene (C ₂₀ ), n-docosane (C ₂₂ , n-tetracoccyme (C ₂₄ ), n-hexacoxy (C ₂₆ ), n-octacoxy (C ₂₈ ) and n-triacontoxy (C ₃₀ ).

C₂ _-6-알킬렌의 예는 에틸렌, 부틸렌, 펜틸렌, 헥실렌 및 2-메틸펜틸렌이다.Examples of C ₂ _-6 -alkylene are ethylene, butylene, pentylene, hexylene and 2-methylpentylene.

C₆ _-14-아릴렌의 예는 모노시클릭 C₆-아릴렌, 예컨대 페닐렌, 비시클릭 C₉ _-10-아릴렌, 예컨대 나프틸렌, 예를 들어C ₆ _-14 - Example of the arylene group is a monocyclic C ₆ -, for arylene, for example naphthylene, e-arylene, for example phenylene, bicyclic C ₉ _-10

,

인데닐렌, 예를 들어Indenylene, for example

,

인다닐렌, 예를 들어Indanylene, for example

,

및 테트라히드로나프틸렌, 예를 들어And tetrahydronaphthylene, for example

,

및 트리시클릭 C₁₂ _-14-아릴렌, 예컨대 안트릴렌, 예를 들어And tricyclic C ₁₂ _-14 -arylene, such as anthrylene, for example

,

페난트릴렌, 예를 들어Phenanthrylene, for example

,

플루오레닐렌, 예를 들어Fluorenylene, for example

,

및And

s-인다세닐렌, 예를 들어s-indacenylene, for example

이다.to be.

C₆ _-24-아릴렌의 예는 C₆ _-14-아릴렌 및 Examples of C ₆ _{-24 -arylene} are C ₆ _-14 -arylene and

,

피레닐렌, 예를 들어Pyrenylene, for example

,

테트라세닐렌, 예를 들어Tetracenylene, for example

,

페릴레닐렌, 예를 들어Perylenylene, for example

,

인데노플루오레닐렌, 예를 들어Indenofluorenylene, for example,

,

펜타세닐렌, 예를 들어Pentacenylene, for example

,

코로네닐렌, 예를 들어Coronenylene, for example

,

및 테트라페닐레닐렌, 예를 들어And tetraphenylenylene, for example

이다.to be.

2가 5 내지 14원 방향족 헤테로시클릭 잔기는 모노시클릭 2가 5 내지 8원 방향족 헤테로시클릭 잔기, 또는 폴리시클릭, 예를 들어 비시클릭 2가 7 내지 14원, 트리시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기, 또는 테트라시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기일 수 있다.Monovalent 5- to 14-membered aromatic heterocyclic residues are monocyclic 2 to 5-to 8-membered aromatic heterocyclic residues, or polycyclic, such as bicyclic 2 is 7 to 14, tricyclic 2 is 9 to 14, Membered aromatic heterocyclic residue, or tetracyclic 2 may be a 9 to 14 membered aromatic heterocyclic residue.

모노시클릭 2가 5 내지 8원 방향족 헤테로시클릭 잔기의 예는 1개의 헤테로원자를 함유하는 모노시클릭 2가 5원 방향족 헤테로시클릭 잔기, 예컨대 피롤릴렌, 푸릴렌 및 티오페닐렌, 2개의 헤테로원자를 함유하는 모노시클릭 2가 5원 방향족 헤테로시클릭 잔기, 예컨대 이미다졸릴렌, 피라졸릴렌, 옥사졸릴렌, 이속사졸릴렌, 티아졸릴렌, 이소티아졸릴렌, 3개의 헤테로원자를 함유하는 모노시클릭 2가 5원 방향족 헤테로시클릭 잔기, 예컨대 1,2,3-트리아졸릴렌, 1,2,4-트리아졸릴렌 및 옥사디아졸릴렌, 4개의 헤테로원자를 함유하는 모노시클릭 2가 5원 방향족 헤테로시클릭 잔기, 예컨대 테트라졸릴렌, 1개의 헤테로원자를 함유하는 모노시클릭 2가 6원 방향족 헤테로시클릭 잔기, 예컨대 피리딜렌, 2개의 헤테로원자를 함유하는 모노시클릭 2가 6원 방향족 헤테로시클릭 잔기, 예컨대 피라지닐렌, 피리미디닐렌 및 피리다지닐렌, 3개의 헤테로원자를 함유하는 모노시클릭 2가 6원 방향족 헤테로시클릭 잔기, 예컨대 1,2,3-트리아지닐렌, 1,2,4-트리아지닐렌 및 1,3,5-트리아지닐렌, 1개의 헤테로원자를 함유하는 모노시클릭 2가 7원 방향족 헤테로시클릭 잔기, 예컨대 아제피닐렌, 및 2개의 헤테로원자를 함유하는 모노시클릭 2가 7원 방향족 헤테로시클릭 잔기, 예컨대 1,2-디아제피닐렌이다.Examples of monocyclic divalent 5-8 membered aromatic heterocyclic residues include monocyclic divalent 5-membered aromatic heterocyclic residues containing one heteroatom such as pyrrolylene, furylene and thiophenylene, two Monocyclic divalent 5-membered aromatic heterocyclic moieties containing heteroatoms such as imidazolylene, pyrazolylene, oxazolylene, isoxazolylene, thiazolylene, isothiazolylene, three heteroatoms Monocyclic divalent 5-membered aromatic heterocyclic moieties containing such as 1,2,3-triazolylene, 1,2,4-triazolylene and oxadiazolylene, mono containing four heteroatoms Cyclic divalent 5-membered aromatic heterocyclic moieties such as tetrazolylene, monocyclic bivalent 6-membered aromatic heterocyclic moieties containing one heteroatom, such as pyridylene, monocylic containing 2 heteroatoms Click divalent 6-membered aromatic hete Cyclic residues such as pyrazinylene, pyrimidinylene and pyridazinylene, monocyclic divalent 6-membered aromatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazinylene, 1 , 2,4-triazinylene and 1,3,5-triazinylene, monocyclic divalent 7-membered aromatic heterocyclic residue containing one heteroatom such as azefinylene, and two heteroatoms Containing monocyclic divalent 7-membered aromatic heterocyclic moieties such as 1,2-diazefinylene.

비시클릭 2가 7 내지 14원 방향족 헤테로시클릭 잔기의 예는Examples of bicyclic 2 to 7 to 14 membered aromatic heterocyclic residues are

2개의 헤테로원자를 함유하는 비시클릭 2가 8원 방향족 헤테로시클릭 잔기, 예컨대 티에노티오페닐렌, 예를 들어Bicyclic 2 containing two heteroatoms is an 8-membered aromatic heterocyclic residue such as thienothiophenylene, for example,

,

3개의 헤테로원자를 함유하는 비시클릭 2가 8원 방향족 헤테로시클릭 잔기, 예컨대 티에노티아졸릴렌, 예를 들어Bicyclic 2 is an 8-membered aromatic heterocyclic residue containing 3 heteroatoms, such as thienothiazolylene, for example

,

4개의 헤테로원자를 함유하는 비시클릭 2가 8원 방향족 헤테로시클릭 잔기, 예컨대 티아조티아졸릴렌, 예를 들어Bicyclic 2 is an 8-membered aromatic heterocyclic residue containing 4 heteroatoms, such as thiazothiazolylenes, for example,

,

1개의 헤테로원자를 함유하는 비시클릭 2가 9원 방향족 헤테로시클릭 잔기, 예컨대 인돌릴렌, 이소인돌릴렌, 인돌리지닐렌, 인돌리닐렌, 이소인돌리닐렌, 예를 들어Bicyclic 2 containing one heteroatom is a 9-membered aromatic heterocyclic residue such as indolylene, isoindolylene, indolizinylene, indolinylene, isoindolinylene, for example,

,

벤조푸릴렌, 이소벤조푸릴렌, 벤조티오페닐렌 및 이소벤조티오페닐렌, Benzofurylene, isobenzofurylene, benzothiophenylene and isobenzothiophenylene,

2개의 헤테로원자를 함유하는 비시클릭 2가 9원 방향족 헤테로시클릭 잔기, 예컨대 인다졸릴렌, 벤즈이미다졸릴렌, 벤즈이미다졸리닐렌, 벤족사졸릴렌, 벤즈이소옥사졸릴렌, 벤즈티아졸릴렌, 벤즈이소티아졸릴렌, 푸로피리딜렌 및 티에노피리딜렌,A bicyclic 2-membered aromatic heterocyclic residue containing two heteroatoms, such as indazolylene, benzimidazolylene, benzimidazolinylene, benzoxazolylene, benzisoxazolylene, benzthiazolyl Isobutylidene, isopentylidene, isopentylidene, isopentylidene,

3개의 헤테로원자를 함유하는 비시클릭 2가 9원 방향족 헤테로시클릭 잔기, 예컨대 벤조트리아졸릴렌, 벤족사디아졸릴렌, 옥사졸로피리딜렌, 이소옥사졸로피리딜렌, 티아졸로피리딜렌, 이소티아졸로피리딜렌, 이미다조피리딜렌, 벤조티아디아졸릴렌, 예를 들어Bicyclic 2 is a 9-membered aromatic heterocyclic residue containing 3 heteroatoms, such as benzotriazolylene, benzoxadiazolylene, oxazopyridylene, isoxazolopyridylene, thiazolopyridylene, isothiazole Pyridylenes, imidazopyridylenes, benzothiadiazolylenes, such as, for example,

,

및 디옥사노티오페닐렌, 예를 들어And dioxanthiophenylene, for example

,

4개의 헤테로원자를 함유하는 비시클릭 2가 9원 방향족 헤테로시클릭 잔기, 예컨대 퓨리닐렌,Bicyclic 2 is a 9-membered aromatic heterocyclic residue containing 4 heteroatoms, such as purinylene,

1개의 헤테로원자를 함유하는 비시클릭 2가 10원 방향족 헤테로시클릭 잔기, 예컨대 퀴놀릴렌, 이소퀴놀릴렌, 크로메닐렌 및 크로마닐렌,Bicyclic 2 is a 10-membered aromatic heterocyclic residue containing one heteroatom such as quinolylene, isoquinolylene, chromenylene and chromanylene,

2개의 헤테로원자를 함유하는 비시클릭 2가 10원 방향족 헤테로시클릭 잔기, 예컨대 퀴녹살리닐렌, 예를 들어Bicyclic 2 containing two heteroatoms is a 10 membered aromatic heterocyclic residue such as quinoxalinylene, e.g.,

,

퀴나졸리닐렌, 신놀리닐렌, 프탈라지닐렌, 1,5-나프티리디닐렌 및 1,8-나프티리디닐렌,Quinazolinylene, cinnolenylene, phthalazienylene, 1,5-naphthyridinylene and 1,8-naphthyridinylene,

3개의 헤테로원자를 함유하는 비시클릭 2가 10원 방향족 헤테로시클릭 잔기, 예컨대 피리도피라지닐렌, 피리도피리미디닐렌 및 피리도피리다지닐렌, 및 4개의 헤테로원자를 함유하는 비시클릭 2가 10원 방향족 헤테로시클릭 잔기, 예컨대 프테리디닐렌이다.Bicyclic 2-membered aromatic heterocyclic residues containing three heteroatoms, such as pyridopyrimidinylene, pyridopyrimidinylene and pyridopyridazinylene, and bicyclic 2 containing four heteroatoms, 10-membered aromatic heterocyclic residue such as pteridinylene.

1개의 헤테로원자를 함유하는 트리시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기의 예는 디벤조푸릴렌, 아크리디닐렌, 디벤조실라시클로펜타디에닐렌, 예를 들어Examples of the tricyclic 2-valent 9 to 14-membered aromatic heterocyclic residue containing one hetero atom include dibenzofurylene, acridinylene, dibenzosilacyclopentadienylene, for example,

,

및 디벤조피롤릴렌, 예를 들어And dibenzopyrrolylene, for example

이다.to be.

2개의 헤테로원자를 함유하는 트리시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기의 예는 페녹사지닐렌, 및 하기 화합물이다.Examples of the tricyclic 2-valent 9 to 14-membered aromatic heterocyclic residue containing two heteroatoms are phenoxazienylene, and the following compounds.

3개의 헤테로원자를 함유하는 트리시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기의 예는 하기 화합물이다.Examples of the tricyclic 2-valent 9 to 14-membered aromatic heterocyclic residue containing three heteroatoms are the following compounds.

4개의 헤테로원자를 함유하는 트리시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기의 예는 하기 화합물이다.Examples of the tricyclic 2-valent 9 to 14-membered aromatic heterocyclic residue containing four heteroatoms are the following compounds.

6개의 헤테로원자를 함유하는 트리시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기의 일례는 하기 화합물이다.An example of a tricyclic 2-valent 9 to 14-membered aromatic heterocyclic residue containing 6 heteroatoms is the following compound.

4개의 헤테로원자를 함유하는 테트라시클릭 2가 9 내지 14원 방향족 헤테로시클릭 잔기의 일례는 하기 화합물이다.An example of a tetracyclic 2-valent 9 to 14-membered aromatic heterocyclic residue containing four heteroatoms is the following compound.

2가 5 내지 24원 방향족 헤테로시클릭 잔기의 예는 2가 5 내지 14원 방향족 헤테로시클릭 잔기, 및 하기 화합물이다.Examples of divalent 5- to 24-membered aromatic heterocyclic moieties are divalent 5- to 14-membered aromatic heterocyclic moieties, and the following compounds.

L의 예는 하기와 같다.An example of L is as follows.

바람직한 화학식 1 및 1'의 단위에서,In preferred units of formulas (1) and (1 '),

R¹은 H, 1 내지 6개의 치환기 R^c로 임의로 치환된 C₁ _-30-알킬, 1 내지 6개의 치환기 R^c로 임의로 치환된 C₂ _-30-알케닐, 1 내지 6개의 치환기 R^c로 임의로 치환된 C_2-30-알키닐, 1 내지 6개의 치환기 R^d로 임의로 치환된 C₃ _-10-시클로알킬, 1 내지 6개의 치환기 R^d로 임의로 치환된 C₅ _-10-시클로알케닐 또는 1 내지 6개의 치환기 R^d로 임의로 치환된 1가 3 내지 14원 지방족 헤테로시클릭 잔기이고, 여기서R ¹ is H, 1-6 substituents R ^c optionally substituted with C ₁ _{-30-a-alkenyl,} 1-6 substituents R ^c - alkyl, one to six substituents R ^c optionally substituted C ₂ to _-30 optionally substituted C _2-30 - alkynyl, 1-6 substituents R ^d with an optionally substituted C ₃ _-10 - cycloalkyl, one to six substituents optionally substituted by R ^d C ₅ _-10 - cycloalkenyl or A monovalent 3- to 14-membered aliphatic heterocyclic residue optionally substituted with one to six substituents R &^lt; ^{d &} gt ;, wherein

R^d는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR², -S-C₁ _-10-알킬, -NH₂, -NHR², -NR²R³, -NH-COR², -COOH, -COOR², -CONH₂, -CONHR², -CONR²R³, -CO-H, -COR², C_1-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^d is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein

X는 C-R⁴이고, 여기서X is CR < ⁴ > wherein

R⁴는 H, 1 내지 6개의 치환기 R^f로 임의로 치환된 C₁ _-30-알킬, 1 내지 6개의 치환기 R^f로 임의로 치환된 C₂ _-30-알케닐, 1 내지 6개의 치환기 R^f로 임의로 치환된 C_2-30-알키닐, 1 내지 6개의 치환기 R^g로 임의로 치환된 C₃ _-10-시클로알킬, 1 내지 6개의 치환기 R^g로 임의로 치환된 C₅ _-10-시클로알케닐 또는 1 내지 6개의 치환기 R^g로 임의로 치환된 1가 3 내지 14원 지방족 헤테로시클릭 잔기이고, 여기서R ⁴ is H, 1 to 6 substituents R ^f optionally substituted with C ₁ _-30-alkyl, one to six substituents R ^f as an optionally substituted C ₂ _{-30-to-alkenyl,} of one to six substituents R ^f optionally substituted C _2-30 - alkynyl, a one to six substituents optionally substituted with R ^g C ₃ _-10 - optionally substituted with cycloalkyl, 1-6 substituents R ^g C ₅ _-10 - cycloalkenyl or A monovalent 3- to 14-membered aliphatic heterocyclic residue optionally substituted with one to six substituents R &^lt; ^g &^gt;, wherein

R^g는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR⁵, -S-C₁ _-10-알킬, -NH₂, -NHR⁵, -NR⁵R⁶, -NH-COR⁵, -COOH, -COOR⁵, -CONH₂, -CONHR⁵, -CONR⁵R⁶, -CO-H, -COR⁵, C_1-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^g is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein

R⁵ 및 R⁶은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C₂ _-10-알키닐, C_3-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C _3-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

R⁸ 및 R⁹는 각 경우에 서로 독립적으로 C₁ _-30-알킬, C₂ _-30-알케닐, C₂ _-30-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁸ and R ⁹ in each case independently of _one another are C ₁ _-30 -alkyl, C ₂ _-30 -alkenyl, C ₂ _-30 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

또는or

이고, 여기서, Where

또는or

L은L is

이고, 여기서, Where

R¹⁶ 및 R¹⁷은 서로 독립적으로 H 또는 C₁ _-30-알킬이고,Alkyl, - R ¹⁶ and R ¹⁷ are independently H or C ₁ _-30 from each other

r은 0, 1 또는 2이고,r is 0, 1 or 2,

n은 5 내지 10,000의 정수이다.and n is an integer of 5 to 10,000.

보다 바람직한 화학식 1 및 1'의 단위에서,In more preferred units of formulas (1) and (1 '),

R¹은 H 또는 1 내지 6개의 치환기 R^c로 임의로 치환된 C₁ _-30-알킬이고, 여기서R ¹ is optionally substituted C ₁ _-30 by H or 1-6 substituents R ^c - alkyl, where

R^c는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR², -S-C₁ _-10-알킬, -NH₂, -NHR², -NR²R³, -NH-COR², -COOH, -COOR², -CONH₂, -CONHR², -CONR²R³, -CO-H, -COR², C_3-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^c is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein

X는 C-R⁴이고, 여기서X is CR < ⁴ > wherein

R⁴는 H 또는 1 내지 6개의 치환기 R^f로 임의로 치환된 C₁ _-30-알킬이고, 여기서R ⁴ is optionally substituted C ₁ _-30 by H or 1-6 substituents R ^f - alkyl, where

R^f는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR⁵, -S-C₁ _-10-알킬, -NH₂, -NHR⁵, -NR⁵R⁶, -NH-COR⁵, -COOH, -COOR⁵, -CONH₂, -CONHR⁵, -CONR⁵R⁶, -CO-H, -COR⁵, C₃ _-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^f is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein

R⁵ 및 R⁶은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C_2-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C_6-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,

또는or

이고, 여기서, Where

또는or

L은L is

이고, 여기서, Where

r은 0, 1 또는 2이고, r is 0, 1 or 2,

n은 5 내지 10,000의 정수이다.and n is an integer of 5 to 10,000.

훨씬 더 바람직한 화학식 1 및 1'의 단위에서,In even more preferred units of formulas (1) and (1 '),

R¹은 1 내지 6개의 치환기 R^c로 임의로 치환된 C₁ _-30-알킬이고, 여기서Alkyl, wherein - R ¹ is optionally substituted C ₁ _-30 with 1 to 6 substituents R ^c

X는 C-R⁴이고, 여기서X is CR < ⁴ > wherein

R^f는 각 경우에 서로 독립적으로 =O, =C(CN)₂, -O-C₂ _-6-알킬렌-O-, 할로겐, -CN, -NO₂, -OH, C₁ _-10-알콕시, -O-CH₂CH₂O-C₁ _-10-알킬, -O-COR⁵, -S-C₁ _-10-알킬, -NH₂, -NHR⁵, -NR⁵R⁶, -NH-COR⁵, -COOH, -COOR⁵, -CONH₂, -CONHR⁵, -CONR⁵R⁶, -CO-H, -COR⁵, C_3-10-시클로알킬, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고, 여기서R ^f is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein

G¹ 및 G²는 서로 독립적으로 1 내지 4개의 치환기 R^a로 임의로 치환된 모노시클릭 2가 5 내지 8원 방향족 헤테로시클릭 잔기이고, 여기서G ¹ and G ² are independently of each other a monocyclic 2 to 5 membered aromatic heterocyclic residue optionally substituted with from 1 to 4 substituents R ^a ,

R¹⁰ 및 R¹¹은 각 경우에 서로 독립적으로 C₁ _-10-알킬, C₂ _-10-알케닐, C_2-10-알키닐, C₃ _-10-시클로알킬, C₅ _-10-시클로알케닐, 1가 3 내지 14원 지방족 헤테로시클릭 잔기, C₆ _-14-아릴 및 1가 5 내지 14원 방향족 헤테로시클릭 잔기로 이루어진 군으로부터 선택되고,R ¹⁰ and R ¹¹ are each independently at each occurrence C ₁ _-10 - alkyl, C ₂ _-10 - alkenyl, C _2-10 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl C _1-6 -alkenyl, monovalent 3- to 14-membered aliphatic heterocyclic moieties, C _6-14 -aryl and monovalent 5- to 14-membered aromatic heterocyclic residues,

L은 1 내지 4개의 치환기 R^b로 임의로 치환된 모노시클릭 2가 5 내지 8원 방향족 헤테로시클릭 잔기이고, 여기서L is monocyclic 2 optionally substituted with one to four substituents R < ^b > is a 5- to 8-membered aromatic heterocyclic residue, wherein

또는or

L은L is

이고, 여기서, Where

r은 0, 1 또는 2이고, r is 0, 1 or 2,

n은 5 내지 10,000의 정수이다.and n is an integer of 5 to 10,000.

가장 바람직한 화학식 1 및 1'의 단위에서,In the most preferred units of formulas (1) and (1 '),

R¹은 C₁ _-30-알킬이고,Alkyl, - R ¹ is C ₁ _-30

X는 C-R⁴이고, 여기서X is CR < ⁴ > wherein

R⁴는 H이고,R < ⁴ > is H,

R^a는 각 경우에 서로 독립적으로 C₁ _-30-알킬이고,R ^a is independently C ₁ _-30 from each other in each case is alkyl,

R^b는 각 경우에 서로 독립적으로 C₁ _-30-알킬이거나,R ^b is in each case independently of _one another C ₁ _-30 -alkyl,

또는or

L은 L is

이고, 여기서, Where

R¹⁶ 및 R¹⁷은 둘 다 H이고,R < ¹⁶ > and R < ¹⁷ > are both H,

q 및 s는 둘 다 1이고,q and s are both 1,

r은 1이고, r is 1,

n은 5 내지 10,000의 정수이다.and n is an integer of 5 to 10,000.

특히 바람직한 화학식 1의 단위는 하기 화학식 1a의 단위이다.Particularly preferred units of formula (1) are those of formula (1a).

<화학식 1a><Formula 1a>

상기 식에서, R¹, X, R^a, L 및 n은 상기에 정의된 바와 같다.Wherein R ¹ , X, R ^a , L and n are as defined above.

특히 바람직한 화학식 1'의 단위는 하기 화학식 1'a의 단위이다.Especially preferred units of formula (1 ') are units of formula (1'a).

<화학식 1'a><Formula 1'a>

특히 바람직한 화학식 1a, 1', 1a 및 1'a의 단위에서,Especially preferred units of formula (1a), (1 '), (1a) and

L은L is

이다.to be.

바람직하게는, n은 5 내지 5,000, 보다 바람직하게는 5 내지 1,000, 보다 더 바람직하게는 5 내지 100, 가장 바람직하게는 10 내지 100의 정수이다.Preferably, n is an integer from 5 to 5,000, more preferably from 5 to 1,000, still more preferably from 5 to 100, and most preferably from 10 to 100.

화학식 1 및 1a의 단위의 특히 바람직한 예는 하기 화학식 1b 및 1c의 단위이다.Particularly preferred examples of the units of the formulas (1) and (1a) are the units of the following formulas (1b) and (1c).

<화학식 1b>&Lt; EMI ID =

상기 식에서, n은 10 내지 1000, 바람직하게는 10 내지 100의 정수이고,Wherein n is an integer from 10 to 1000, preferably from 10 to 100,

<화학식 1c>&Lt; Formula 1c >

상기 식에서, n은 10 내지 1000, 바람직하게는 10 내지 100의 정수이다.In the above formula, n is an integer of 10 to 1000, preferably 10 to 100.

화학식 1' 및 1'a의 단위의 특히 바람직한 예는 하기 화학식 1'b 및 1'c의 단위이다.Particularly preferred examples of the units of the formulas (1 ') and (1' a) are the units of the following formulas (1b) and (1c).

<화학식 1'b><Formula 1'b>

상기 식에서, n은 10 내지 1000, 바람직하게는 10 내지 100의 정수이고, Wherein n is an integer from 10 to 1000, preferably from 10 to 100,

<화학식 1'c>&Lt; Formula 1 &

본 발명의 반도체 물질은, 중합체의 중량을 기준으로 하여, 바람직하게는 80 중량% 이상, 보다 바람직하게는 90 중량% 이상의 화학식 1 및/또는 1', 1a 및/또는 1'a의 단위를 각각 포함하는 중합체일 수 있다.The semiconductor material of the present invention preferably comprises at least 80 wt%, more preferably at least 90 wt% of units of formula (1) and / or 1 ', 1 a and / or 1'a, based on the weight of the polymer Containing polymer.

가장 바람직하게는, 본 발명의 반도체 물질은 본질적으로 각각 화학식 1 및/또는 1', 1a 및/또는 1'a의 단위로 이루어진 중합체이다.Most preferably, the semiconductor material of the present invention is a polymer consisting essentially of units of formula 1 and / or 1 ', 1a and / or 1'a, respectively.

화학식 1 및/또는 1'의 단위를 포함하는 중합체는 당업계에 공지된 방법에 의해 제조될 수 있다.Polymers comprising units of formulas (1) and / or (1 ') can be prepared by methods known in the art.

화학식 1 및/또는 1'의 단위를 포함하는 중합체는, 예를 들어, 하기 화학식 2의 화합물을 전이 금속 촉매 1의 존재 하에 하기 화학식 3의 화합물로 처리함으로써 제조될 수 있다.Polymers comprising units of formulas (1) and / or (1 ') can be prepared, for example, by treating a compound of formula (2): in the presence of a transition metal catalyst 1 with a compound of formula

<화학식 2>(2)

상기 식에서, R¹ 및 X는 상기에 정의된 바와 같고, Hal은 할로겐, 바람직하게는 -Br이고,Wherein R ¹ and X are as defined above, Hal is halogen, preferably -Br,

<화학식 3><Formula 3>

상기 식에서, G¹, G², L, q, r 및 s는 상기에 정의된 바와 같고, R¹⁰⁰, R¹⁰¹ 및 R¹⁰²는 서로 독립적으로 C₁ _-10-알킬, 바람직하게는 메틸이다.Wherein R ¹ , R ¹⁰¹ and R ¹⁰² independently of _one another are C ₁ _-10 -alkyl, preferably methyl. In the above formula, G ¹ , G ² , L, q, r and s are as defined above.

바람직하게는 전이 금속 촉매 1은, 바람직하게는 포스핀, 예컨대 트리-o-톨릴포스핀과 조합된 팔라듐 촉매, 예컨대 트리스(디벤질리덴아세톤)디팔라듐(0)이다. 반응은 바람직하게는 승온, 예컨대 80 내지 200℃, 바람직하게는 90 내지 150℃에서 수행된다. 반응은 불활성 유기 용매, 예컨대 클로로벤젠 중에서 수행될 수 있다. 반응은 말단 캡퍼, 예컨대 2-브로모티오펜 및 2-트리부틸스태닐티오펜의 첨가에 의해 중단될 수 있다. 조 생성물을 통상적인 방법에 의해, 예를 들어 조 생성물을 적절한 용매, 예를 들어 아세톤으로 추출함으로써 후처리할 수 있다.Preferably, the transition metal catalyst 1 is a palladium catalyst, preferably tris (dibenzylideneacetone) dipalladium (0), preferably in combination with a phosphine such as tri-o-tolylphosphine. The reaction is preferably carried out at elevated temperatures such as 80 to 200 ° C, preferably 90 to 150 ° C. The reaction can be carried out in an inert organic solvent such as chlorobenzene. The reaction can be stopped by addition of a terminal capper such as 2-bromothiophene and 2-tributylstannylthiophene. The crude product can be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, such as acetone.

화학식 2의 화합물은 하기 화학식 4의 화합물을 전이 금속 촉매 2로 처리함으로써 제조될 수 있다.The compound of formula (2) may be prepared by treating a compound of formula (4) with a transition metal catalyst (2).

<화학식 4>&Lt; Formula 4 >

상기 식에서, R¹, X 및 Hal은 상기에 정의된 바와 같다.Wherein R ¹ , X and Hal are as defined above.

전이 금속 촉매 2는 바람직하게는 구리이다. 반응은 바람직하게는 승온, 예컨대 80 내지 150℃, 바람직하게는 100 내지 120℃에서 수행된다. 반응은 불활성 유기 용매, 예컨대 디메틸포름아미드 중에서 수행될 수 있다. 조 생성물을 통상적인 방법에 의해, 예를 들어 조 생성물을 적절한 용매, 예를 들어 디에틸에테르로 추출함으로써 후처리할 수 있다.The transition metal catalyst 2 is preferably copper. The reaction is preferably carried out at an elevated temperature, for example 80 to 150 ° C, preferably 100 to 120 ° C. The reaction can be carried out in an inert organic solvent such as dimethylformamide. The crude product can be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, such as diethyl ether.

화학식 4의 화합물은 하기 화학식 5의 화합물을 할로겐화제로 처리함으로써 제조될 수 있다.The compound of formula (4) can be prepared by treating a compound of formula (5) with a halogenating agent.

<화학식 5>&Lt; Formula 5 >

상기 식에서, R¹ 및 X는 상기에 정의된 바와 같다.Wherein R ¹ and X are as defined above.

할로겐화제는 바람직하게는 N-브로모숙신이미드이다. 반응은 바람직하게는 약간 승온, 예컨대 35 내지 80℃, 바람직하게는 40 내지 60℃에서 수행된다. 반응은 유기 용매, 예컨대 클로로포름/아세트산 중에서 수행될 수 있다. 조 생성물을 통상적인 방법에 의해, 예를 들어 조 생성물을 적절한 용매, 예를 들어 디클로로메탄으로 추출함으로써 후처리할 수 있다.The halogenating agent is preferably N-bromosuccinimide. The reaction is preferably carried out at a slightly elevated temperature, for example 35 to 80 占 폚, preferably 40 to 60 占 폚. The reaction may be carried out in an organic solvent such as chloroform / acetic acid. The crude product can be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, such as dichloromethane.

화학식 5의 화합물은 하기 화학식 6의 화합물을 염기의 존재 하에 하기 화학식 7의 화합물과 반응시킴으로써 제조될 수 있다.The compound of formula (5) can be prepared by reacting a compound of formula (6) with a compound of formula (7) in the presence of a base.

<화학식 6>(6)

상기 식에서, R¹ 및 X는 상기에 정의된 바와 같고,Wherein R < ¹ > and X are as defined above,

<화학식 7>&Lt; Formula 7 >

상기 식에서, X는 상기에 정의된 바와 같고, LG¹은 이탈기, 바람직하게는 -Cl이다.Wherein X is as defined above and LG ¹ is a leaving group, preferably -Cl.

염기는 바람직하게는 3급 아민, 예컨대 트리에틸아민이다. 반응은 바람직하게는 약간 승온, 예컨대 35 내지 80℃, 바람직하게는 40 내지 60℃에서 수행된다. 반응은 유기 용매, 예컨대 클로로포름/아세트산 중에서 수행될 수 있다. 조 생성물을 통상적인 방법에 의해, 예를 들어 조 생성물을 적절한 용매, 예를 들어 디클로로메탄으로 추출함으로써 후처리할 수 있다.The base is preferably a tertiary amine, such as triethylamine. The reaction is preferably carried out at a slightly elevated temperature, for example 35 to 80 占 폚, preferably 40 to 60 占 폚. The reaction may be carried out in an organic solvent such as chloroform / acetic acid. The crude product can be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, such as dichloromethane.

화학식 2, 4 및 5의 화합물 또한 본 발명의 일부이다.The compounds of formulas (2), (4) and (5) are also part of the present invention.

반도체 물질로서 화학식 1 및/또는 1'의 단위를 포함하는 중합체를 포함하는 전자 소자 또한 본 발명의 일부이다. 바람직하게는, 전자 소자는 유기 전계 효과 트랜지스터 (OFET), 또한 특히 박막 트랜지스터 (TFT)이다. 바람직하게는, 전자 소자는 유기 광기전 소자 (OPV)이다.An electronic device comprising a polymer comprising units of formula (1) and / or (1 ') as a semiconductor material is also part of the present invention. Preferably, the electronic device is an organic field effect transistor (OFET), especially also a thin film transistor (TFT). Preferably, the electronic device is an organic photovoltaic device (OPV).

통상적으로, 유기 전계 효과 트랜지스터는 유전체 층, 반도체 층 및 기판을 포함한다. 또한, 유기 전계 효과 트랜지스터는 통상적으로 게이트 전극 및 소스/드레인 전극을 포함한다.Typically, the organic field effect transistor comprises a dielectric layer, a semiconductor layer and a substrate. Further, the organic field effect transistor typically includes a gate electrode and a source / drain electrode.

유기 전계 효과 트랜지스터는 다양한 디자인을 가질 수 있다.Organic field effect transistors can have a variety of designs.

전계-효과 트랜지스터의 가장 통상적인 디자인은 바텀-게이트 탑-콘택트(Bottom-Gate Top-Contact) (BGTC) 디자인이다. 여기서, 게이트는 기판의 상단 및 유전체 층의 저부에 있고, 반도체 층은 유전체 층의 상단에 있고, 소스/드레인 전극은 반도체 층의 상단에 있다.The most common design of field-effect transistors is the Bottom-Gate Top-Contact (BGTC) design. Here, the gate is at the top of the substrate and the bottom of the dielectric layer, the semiconductor layer is at the top of the dielectric layer, and the source / drain electrode is at the top of the semiconductor layer.

전계-효과 트랜지스터의 또 다른 디자인은 탑-게이트 바텀-콘택트(Top-Gate Bottom-Contact) (TGBC) 디자인이다. 여기서, 소스/드레인 전극은 기판의 상단 및 반도체 층의 저부에 있고, 유전체 층은 반도체 층의 상단에 있고, 게이트 전극은 유전체 층의 상단에 있다.Another design of the field-effect transistor is the Top-Gate Bottom-Contact (TGBC) design. Here, the source / drain electrode is at the top of the substrate and the bottom of the semiconductor layer, the dielectric layer is at the top of the semiconductor layer, and the gate electrode is at the top of the dielectric layer.

반도체 층은 본 발명의 반도체 물질을 포함한다. 반도체 층은 5 내지 500 nm, 바람직하게는 10 내지 100 nm, 보다 바람직하게는 20 내지 50 nm의 두께를 가질 수 있다.The semiconductor layer comprises the semiconductor material of the present invention. The semiconductor layer may have a thickness of 5 to 500 nm, preferably 10 to 100 nm, more preferably 20 to 50 nm.

유전체 층은 유전체 물질을 포함한다. 유전체 물질은 실리슘/이산화실리슘, 또는 바람직하게는, 유기 중합체, 예컨대 폴리스티렌 (PS), 폴리(메틸메타크릴레이트) (PMMA), 폴리(4-비닐페놀) (PVP), 폴리(비닐 알콜) (PVA), 안조시클로부텐 (BCB), 또는 폴리이미드 (PI)일 수 있다. 유전체 층은 10 내지 2000 nm, 바람직하게는 50 내지 1000 nm, 보다 바람직하게는 100 내지 800 nm의 두께를 가질 수 있다.The dielectric layer includes a dielectric material. The dielectric material may be selected from the group consisting of silica / silicon dioxide, or preferably organic polymers such as polystyrene (PS), poly (methyl methacrylate) (PMMA), poly (4-vinyl phenol) (PVA), anisocyclobutene (BCB), or polyimide (PI). The dielectric layer may have a thickness of 10 to 2000 nm, preferably 50 to 1000 nm, more preferably 100 to 800 nm.

소스/드레인 콘택트 및 게이트 콘택트는 임의의 적합한 물질, 예를 들어 Au로부터 형성될 수 있다.The source / drain contacts and the gate contacts may be formed from any suitable material, for example Au.

기판은 임의의 적합한 기판, 예컨대 유리, 또는 플라스틱 기판일 수 있다. 바람직하게는 기판은 플라스틱 기판, 예컨대 폴리에테르술폰, 폴리카르보네이트, 폴리술폰, 폴리에틸렌 테레프탈레이트 (PET) 및 폴리에틸렌 나프탈레이트 (PEN)이다. 보다 바람직하게는, 플라스틱 기판은 플라스틱 호일이다.The substrate can be any suitable substrate, such as glass, or a plastic substrate. Preferably, the substrate is a plastic substrate such as polyethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). More preferably, the plastic substrate is a plastic foil.

유기 전계 효과 트랜지스터는 당업계에 공지된 방법에 의해 제조될 수 있다.Organic field effect transistors can be prepared by methods known in the art.

예를 들어, 탑-게이트 바텀-콘택트 (TGBC) 박막 트랜지스터 (TFT)는 하기와 같이 제조될 수 있다: 첫번째로, 소스/드레인 콘택트를, 예를 들어 소스/드레인 물질의 열 증발에 의해, 기판 상에 배치하고; 두번째로, 예를 들어 적합한 용매 중의 반도체 물질의 용액을 스핀-코팅하고 반도체 층을 승온, 예를 들어 80 내지 100℃에서 건조시킴으로써, 기판을 반도체 층으로 코팅하고; 세번째로, 예를 들어 유전체 물질의 용액을 스핀-코팅하고 유전체 층을 승온, 예를 들어 80 내지 100℃에서 건조시킴으로써, 반도체 층을 적합한 용매 중의 유전체 물질의 용액으로 코팅하고; 네번째로, 게이트 콘택트를, 예를 들어 게이트 물질의 열 증발에 의해, 유전체 층의 상단에 배치한다.For example, a top-gate bottom-contact (TGBC) thin film transistor (TFT) can be fabricated as follows: First, the source / drain contacts are formed by thermal evaporation of, for example, Lt; / RTI > Second, the substrate is coated with a semiconductor layer, for example, by spin-coating a solution of the semiconductor material in a suitable solvent and drying the semiconductor layer at elevated temperature, e.g., 80 to 100 占 폚; Third, the semiconductor layer is coated with a solution of the dielectric material in a suitable solvent, for example by spin-coating a solution of the dielectric material and drying the dielectric layer at elevated temperature, e.g., 80-100 占 폚; Fourth, the gate contacts are placed at the top of the dielectric layer, for example by thermal evaporation of the gate material.

화학식 1 및/또는 1'의 단위를 포함하는 중합체의 반도체 물질로서의 용도 또한 본 발명의 일부이다.The use of polymers comprising units of formula (1) and / or (1 ') as semiconductor materials is also part of the present invention.

본 발명의 반도체 물질을 포함하는 전자 소자는 높은 전하 캐리어 이동도 뿐만 아니라, 주위 환경 조건 하에, 특히 공기에 의한 산화에 대해 높은 안정성을 나타낸다.The electronic device comprising the semiconductor material of the present invention exhibits high stability against oxidation by air, especially under ambient environmental conditions, as well as high charge carrier mobility.

또한, 본 발명의 반도체 물질은, 액체 가공 기술, 예컨대 스핀 코팅과 상용성이고, 따라서 저비용의, 경량이고 유연한 전자 소자의 제조를 가능하게 한다.In addition, the semiconductor material of the present invention is compatible with liquid processing techniques such as spin coating, thus making it possible to produce low cost, lightweight and flexible electronic devices.

실시예Example

모든 시약은 상업적 공급원으로부터 구입하였고, 달리 언급되지 않는 한 추가 정제 없이 사용하였다. 통상적인 슈렝크(Schlenk) 기술을 이용하였고, 달리 언급되지 않는 한 반응을 N₂ 하에 수행하였다. NMR 스펙트럼은 바리안(Varian) 400MR 분광측정계 (¹H, 400 MHz) 상에서 기록하였다. 중합체 분자량은, 폴리스티렌 기준물에 대하여 실온에서 THF 중에서 굴절률 검출기를 이용하여 애질런트(Agilent) 1200 시리즈에서 측정하였다.All reagents were purchased from commercial sources and used without further purification unless otherwise stated. The usual Schlenk technique was used and the reaction was carried out under N ₂ unless otherwise stated. NMR spectra were recorded on a Varian 400 MR spectrometer ( ¹ H, 400 MHz). Polymer molecular weights were measured in an Agilent 1200 series using refractive index detectors in THF at room temperature against polystyrene standards.

실시예 1Example 1

3-도데실아미노티오펜 (6a)의 제조Preparation of 3-dodecylaminothiophene (6a)

3-브로모티오펜 (7.20 g, 44.16 mmol), 도데실아민 (12.28 g, 166.24 mmol), Cu (0.14 g, 2.21 mmol), CuI (0.42 g, 2.21 mmol), K₃PO₄ (18.75 g, 88.32 mmol), 및 N,N-디메틸에탄올아민 (60 mL)의 혼합물을 N₂ 퍼징하였다. 이어서, 반응 혼합물을 질소 하에 90℃에서 2일 동안 교반하였다. 반응 혼합물을 물로 켄칭시키고, 디에틸 에테르로 추출한 후, 염수로 세척하였다. 유기 층을 Na₂SO₄ 상에서 건조시켰다. 조 화합물을, 용리액으로서 헥산 중 0 내지 5% 에틸 아세테이트를 사용하여 실리카 겔 상 칼럼 크로마토그래피에 의해 정제하여, 3-도데실아미노티오펜 (6a)을 갈색 고체로서 수득하였다 (5.75 g, 49%).3-bromothiophene (7.20 g, 44.16 mmol), dodecylamine (12.28 g, 166.24 mmol), Cu (0.14 g, 2.21 mmol), CuI (0.42 g, 2.21 mmol), K 3 PO 4 (18.75 g, 88.32 mmol), and N, N-dimethylethanolamine (60 mL) was N ₂ purged. The reaction mixture was then stirred at 90 < 0 > C under nitrogen for 2 days. The reaction mixture was quenched with water, extracted with diethyl ether, and washed with brine. The organic layer was dried over Na ₂ SO _4. The crude compound was purified by column chromatography on silica gel using 0-5% ethyl acetate in hexanes as eluent to give 3-dodecylaminothiophene (6a) as a brown solid (5.75 g, 49% ).

실시예 2Example 2

3-티오펜카르보닐클로라이드 (7a)의 제조Preparation of 3-thiophenecarbonyl chloride (7a)

3-티오펜카르복실산 (3.50 g, 27.31 mmol) 및 톨루엔 (80 mL)을 둥근 바닥 플라스크에 첨가하였다. 이어서, 옥살릴 클로라이드 (3.57 mL, 40.97 mmol) 및 DMF (1 액적)을 혼합물에 첨가하였다. 반응 혼합물을 밤새 80℃에서 가열하였다. 용매를 진공 하에 제거하고, 남아있는 조 고체를 톨루엔 중에 용해시키고, 수소화칼슘 상에서 건조시킨 후, 용매를 증발시켰다. 3-티오펜카르보닐클로라이드 (7a)는 갈색 고체였고 (3.02 g, 75.43%), 이를 추가 정제 없이 실시예 3에서 직접 사용하였다.3-Thiophenecarboxylic acid (3.50 g, 27.31 mmol) and toluene (80 mL) were added to a round bottom flask. Oxalyl chloride (3.57 mL, 40.97 mmol) and DMF (1 drop) were then added to the mixture. The reaction mixture was heated at 80 < 0 > C overnight. The solvent was removed in vacuo and the remaining crude was dissolved in toluene, dried over calcium hydride and the solvent was evaporated. 3-Thiophenecarbonyl chloride (7a) was a brown solid (3.02 g, 75.43%) which was used directly in Example 3 without further purification.

실시예 3Example 3

화합물 5a의 제조Preparation of Compound 5a

3-도데실아미노티오펜 (6a) (5.62 g, 21.01 mmol), THF (40 mL), 및 트리에틸아민 (3.87 g, 38.20 mmol)을 질소 하에 둥근 바닥 플라스크에 첨가하였다. 0℃에서, THF (20 mL) 중 3-티오펜카르보닐클로라이드 (7a) (2.80 g, 19.10 mmol)를 적가하였다. 이어서, 반응 혼합물을 실온으로 가온시키고, 밤새 교반하였다. 혼합물을 물에 붓고, 디클로로메탄으로 추출하였다. 유기 층을 Na₂SO₄ 상에서 건조시켰다. 조 화합물을, 용리액으로서 헥산 중 0 내지 10% 에틸 아세테이트를 사용하여 실리카 겔 상 칼럼 크로마토그래피에 의해 정제하여, 화합물 5a를 밝은 갈색 고체로서 수득하였다 (6.1 g, 84.6%). 3-Dodecylaminothiophene (6a) (5.62 g, 21.01 mmol), THF (40 mL), and triethylamine (3.87 g, 38.20 mmol) were added to a round bottom flask under nitrogen. At 0 < 0 > C, 3-thiophenecarbonyl chloride 7a (2.80 g, 19.10 mmol) in THF (20 mL) was added dropwise. The reaction mixture was then allowed to warm to room temperature and stirred overnight. The mixture was poured into water and extracted with dichloromethane. The organic layer was dried over Na ₂ SO _4. The crude compound was purified by column chromatography on silica gel using 0-10% ethyl acetate in hexanes as eluent to give compound 5a as a light brown solid (6.1 g, 84.6%).

실시예 4Example 4

화합물 4a의 제조Preparation of compound 4a

화합물 5a (6.0 g, 15.89 mmol)를 클로로포름 (150 mL)/아세트산 (50 mL) 혼합물 중에 용해시켰다. 플라스크를 알루미늄 호일로 감싸 반응 혼합물을 빛으로부터 보호하였다. N-브로모숙신이미드 (11.31 g, 63.56 mmol)를 첨가하고, 반응 혼합물을 실온에서 2시간 동안 교반한 후, 50℃에서 교반하였다. 반응을 박층 크로마토그래피에 의해 모니터링하였다. 반응이 완료될 때까지 추가량의 NBS를 첨가하였다. 물을 첨가하여 반응 혼합물을 켄칭시키고, 반응 혼합물을 디클로로메탄으로 추출하였다. 유기 층을 Na₂SO₄ 상에서 건조시켰다. 조 화합물 4a를, 용리액으로서 헥산 중 0 내지 60% 디클로로메탄을 사용하여 실리카 겔 상 칼럼 크로마토그래피에 의해 정제하여, 화합물 4a를 녹색 액체로서 수득하였다 (4.8 g, 42.7%).Compound 5a (6.0 g, 15.89 mmol) was dissolved in a mixture of chloroform (150 mL) / acetic acid (50 mL). The flask was wrapped with aluminum foil to protect the reaction mixture from light. N-Bromosuccinimide (11.31 g, 63.56 mmol) was added and the reaction mixture was stirred at room temperature for 2 hours and then at 50 < 0 > C. The reaction was monitored by thin layer chromatography. An additional amount of NBS was added until the reaction was complete. The reaction mixture was quenched by addition of water and the reaction mixture was extracted with dichloromethane. The organic layer was dried over Na ₂ SO _4. The crude compound 4a was purified by column chromatography on silica gel using 0-60% dichloromethane in hexanes as eluent to give 4a as a green liquid (4.8 g, 42.7%).

실시예 5Example 5

화합물 2a의 제조Preparation of Compound 2a

Cu (0.348 g, 5.48 mmol)를 N₂ 하에 둥근 바닥 플라스크에 첨가하였다. DMF (260 mL) 중 화합물 4a (3.80 g, 5.48 mmol)를 첨가하고, 반응 혼합물을 110℃에서 밤새 교반하였다. 반응을 박층 크로마토그래피에 의해 모니터링하였다. 추가의 Cu를 첨가하여 반응을 완료시켰다. 반응 혼합물을 물로 켄칭시키고, 디에틸에테르로 추출하였다. 유기 층을 물로 세척하고, Na₂SO₄ 상에서 건조시켰다. 조 화합물 2a를, 용리액으로서 헥산 중 0 내지 70% 디클로로메탄을 사용하여 실리카 겔 상 칼럼 크로마토그래피에 의해 정제하여, 화합물 2a를 갈색 고체로서 수득하였다 (0.44 g, 15.0%).A Cu (0.348 g, 5.48 mmol) was added under N ₂ to the round bottom flask. Compound 4a (3.80 g, 5.48 mmol) in DMF (260 mL) was added and the reaction mixture was stirred overnight at 110 <0> C. The reaction was monitored by thin layer chromatography. Additional Cu was added to complete the reaction. The reaction mixture was quenched with water and extracted with diethyl ether. The organic layer was washed with water, dried over Na ₂ SO _4. The crude compound 2a was purified by column chromatography on silica gel using 0-70% dichloromethane in hexanes as eluent to give compound 2a as a brown solid (0.44 g, 15.0%).

실시예 6Example 6

본질적으로 화학식 1b 및/또는 1'b의 단위로 이루어진 중합체 P1의 제조Preparation of polymer P1 consisting essentially of units of formula < RTI ID = 0.0 > Ib <

화합물 3a (0.11 g, 0.13 mmol), 트리스(디벤질리덴아세톤)디팔라듐(0) (Pd₂dba₃) (0.0036 g, 0.004 mmol), 및 P(o-톨릴)₃ (0.0024 g, 0.008 mmol)을 둥근 바닥 플라스크에 첨가하고, N₂ 퍼징하였다. 이어서, 클로로벤젠 (2.5 mL) 중 화합물 2a (0.07 g, 0.13 mmol)를 첨가하고, 혼합물을 130℃에서 교반하였다. 2-브로모티오펜 및 2-트리부틸스태닐티오펜을 첨가하여 본질적으로 화학식 1b 및/또는 1'b의 단위로 이루어진 중합체를 말단 캡핑한 후, 메탄올 중에서 침전시키고 여과하였다. 아세톤으로 밤새 속슬렛(Soxhlet) 추출한 후, 본질적으로 화학식 1b 및/또는 1'b의 단위로 이루어진 중합체 P1을 클로로벤젠 중에 용해시키고, 메탄올 중에서 재침전시켰다. 본질적으로 화학식 1b 및/또는 1'b의 단위로 이루어진 최종 중합체 P1은 갈색 고체였다 (105 mg). Mn = 1.83 × 10⁴ g/mol, D = 8.6. Compound 3a (0.11 g, 0.13 mmol) , tris (dibenzylideneacetone) dipalladium _{_{(0) (Pd 2 dba 3}} ) (0.0036 g, 0.004 mmol), and P (o- tolyl) ₃ (0.0024 g, 0.008 mmol ) Was added to a round bottom flask and purged with N ₂ . Compound 2a (0.07 g, 0.13 mmol) in chlorobenzene (2.5 mL) was then added and the mixture was stirred at 130 < 0 > C. 2-bromothiophene and 2-tributylstannylthiophene were added to end-capped the polymer consisting essentially of units of formula (Ib) and / or 1'b, followed by precipitation in methanol and filtration. After Soxhlet extraction with acetone overnight, polymer P1 consisting essentially of units of formulas 1b and / or 1'b was dissolved in chlorobenzene and reprecipitated in methanol. The final polymer P1 consisting essentially of units of formula (Ib) and / or 1'b was a brown solid (105 mg). Mn = 1.83 × 10 ⁴ g / mol, D = 8.6.

실시예 7Example 7

본질적으로 화학식 1c 및/또는 1'c의 단위로 이루어진 중합체 P2의 제조Preparation of polymer P2 consisting essentially of units of formula < RTI ID = 0.0 > 1c <

화합물 2a (0.10 g, 0.19 mmol), 트리스(디벤질리덴아세톤)디팔라듐(0) (Pd₂dba₃) (0.0052 g, 0.006 mmol), 및 P(o-톨릴)₃ (0.0034 g, 0.011 mmol)을 둥근 바닥 플라스크에 첨가하고, N₂ 퍼징하였다. 이어서, 클로로벤젠 (7 mL) 중 화합물 3b (0.17 g, 0.19 mmol)를 첨가하고, 혼합물을 130℃에서 교반하였다. 2-브로모티오펜 및 2-트리부틸스태닐티오펜을 첨가하여 본질적으로 화학식 1c 및/또는 1'c의 단위로 이루어진 중합체를 말단 캡핑한 후, 메탄올 중에서 침전시키고 여과하였다. 아세톤으로 밤새 속슬렛 추출한 후, 본질적으로 화학식 1c 및/또는 1'c의 단위로 이루어진 중합체 P2를 클로로벤젠 중에 용해시키고, 메탄올 중에서 재침전시켰다. 본질적으로 화학식 1c 및/또는 1'c의 단위로 이루어진 최종 중합체 P2는 갈색 고체였다 (150 mg). Mn = 1.64 × 10⁴ g/mol, D = 3.3. Compound 2a (0.10 g, 0.19 mmol) , tris (dibenzylideneacetone) dipalladium _{_{(0) (Pd 2 dba 3}} ) (0.0052 g, 0.006 mmol), and P (o- tolyl) ₃ (0.0034 g, 0.011 mmol ) Was added to a round bottom flask and purged with N ₂ . Compound 3b (0.17 g, 0.19 mmol) in chlorobenzene (7 mL) was then added and the mixture was stirred at 130 < 0 > C. 2-bromothiophene and 2-tributylstannylthiophene were added to end-capper the polymer consisting essentially of units of formula (Ic) and / or 1'C, followed by precipitation in methanol and filtration. After Soxhlet extraction overnight with acetone, polymer P2 consisting essentially of units of formula (Ic) and / or 1'c was dissolved in chlorobenzene and reprecipitated in methanol. The final polymer P2, consisting essentially of units of formula (1c) and / or 1'c, was a brown solid (150 mg). Mn = 1.64 × 10 ⁴ g / mol, D = 3.3.

실시예 8Example 8

반도체 물질로서 중합체 P1, P2를 각각 함유하는 탑-게이트 바텀-콘택트 트랜지스터 (TGBC)의 제조Manufacturing a top-gate bottom-contact transistor (TGBC) containing polymers P1 and P2, respectively, as a semiconductor material

탑-게이트 바텀-콘택트 (TGBC) 박막 트랜지스터 (TFT)를 유리 (PGO 유리를 공급받은 상태 그대로 사용함) 상에 제작하였다. Au 소스-드레인 콘택트 (30 nm-두께)를 열 증발시켰다. 이어서, 기판을, 톨루엔 중 각각 중합체 P1, P2의 용액 (농도 ~ 10 mg/mL)을 스핀-코팅 (1500 rpm)하고, 필름을 90℃에서 30초 동안 건조시킴으로써, 반도체 층 (두께: 30 내지 40 nm)으로 코팅하였다. 이소프로필아세테이트 중 4 중량% 폴리스티렌 용액을 스핀-코팅 (3600 rpm)하고, 형성된 유전체 필름을 90℃에서 30초 동안 건조시켜 유전체 층 (두께: 500 내지 600 nm)을 얻었다. 섀도우 마스크를 통한 패턴화된 Au 게이트 콘택트 (~30 nm 두께)의 증착에 의해 소자 구조를 완성하였다. 채널 길이 및 폭은 각각 50 ㎛ 및 0.5 mm였고, 이로부터 W/L = 10을 얻었다.A top-gate bottom-contact (TGBC) thin film transistor (TFT) was fabricated on glass (using PGO glass as supplied). Au source-drain contacts (30 nm-thick) were thermally evaporated. Subsequently, the substrate was spin-coated (1500 rpm) with a solution (concentration ~ 10 mg / mL) of each of the polymers P1 and P2 in toluene and the film was dried at 90 DEG C for 30 seconds, 40 nm). A 4 wt% polystyrene solution in isopropyl acetate was spin-coated (3600 rpm), and the formed dielectric film was dried at 90 캜 for 30 seconds to obtain a dielectric layer (thickness: 500 to 600 nm). The device structure was completed by deposition of patterned Au gate contacts (~ 30 nm thick) through a shadow mask. The channel length and width were 50 탆 and 0.5 mm, respectively, from which W / L = 10 was obtained.

실시예 8의 탑-게이트, 바텀-콘택트 (TGBC) 박막 트랜지스터는 하기 이동도를 나타내었다.The top-gate, bottom-contact (TGBC) thin film transistor of Example 8 showed the following mobility.

P1: 이동도 = 1.5 × 10^-3 cm²V^-1s^-1,P1: mobility = 1.5 × 10 ^-3 cm ² V ^-1 s ^-1 ,

P2: 이동도 = 1.3 × 10^-3 cm²V^-1s^-1.P2: mobility = 1.3 × 10 ^-3 cm ² V ^-1 s ^-1 .

Claims

A polymer comprising a unit of formula 1 and / or formula 1 ′.
&Lt; Formula 1 >

&Lt; Formula (1) >

In this formula,
R ¹ is H, 1-6 substituents R ^c optionally substituted with C ₁ _{-30-a-alkenyl,} 1-6 substituents R ^c - alkyl, one to six substituents R ^c optionally substituted C ₂ to _-30 optionally substituted C _2-30 - alkynyl, 1-6 substituents R ^d, optionally substituted C ₃ _-10 by-cycloalkyl, 1-6 substituents R ^d optionally substituted with C ₅ _{-10-cycloalkenyl,} optionally substituted with aryl, or 1-6 substituents R ^e - 1 to 6 substituents R ^d with an optionally substituted 1, 3 to 14-membered aliphatic heterocyclic moiety, 1 to 6 in the substituent R ^e is optionally substituted C ₆ _-14 Substituted monovalent 5- to 14-membered aromatic heterocyclic moiety, wherein
R ^c is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-10 -alkyl, -O-COR ² , -SC ₁ _-10 -alkyl, -NH ₂ , -NHR ² , -NR ² R ³ , -NH-COR ² , -COOH , -COOR ² , -CONH ₂ , -CONHR ² , -CONR ² R ³ , -CO-H, -COR ² , C _3-10 -cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic moiety, C ₆ _-14 -aryl and _{monovalent 5-14} membered aromatic heterocyclic moiety;
R ^d is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , _-14 C ₆ - is selected from aryl, and the group 1 is made of a 5- to 14-membered aromatic heterocyclic residue,
R ^e is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residues, wherein
R ² and R ³ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C _3-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
X is N or CR < ⁴ >, wherein
R ⁴ is H, 1 to 6 substituents R ^f optionally substituted with C ₁ _-30-alkyl, one to six substituents R ^f as an optionally substituted C ₂ _{-30-to-alkenyl,} of one to six substituents R ^f optionally substituted C _2-30 - alkynyl, 1-6 substituents R ^g optionally substituted C ₃ _-10 by-cycloalkyl, 1-6 substituents R ^g optionally substituted with C ₅ _{-10-cycloalkenyl,} 1 to 6 substituents R ^g as optionally substituted monovalent aliphatic 3-to 14-membered heterocyclic residue with 1 to 6 substituents R ^h, optionally substituted C ₆ _-14 a-aryl, or 1-6 substituents R ^h, optionally Substituted monovalent 5- to 14-membered aromatic heterocyclic moiety, wherein
R ^f is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,
R ^g is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , _-14 C ₆ - is selected from aryl, and the group 1 is made of a 5- to 14-membered aromatic heterocyclic residue,
R ^h is independently from each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 1-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residues, wherein
R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
G ¹ and G ² are independently of one to six substituents R ^a as an optionally substituted C ₆ _-14 each other arylene or 1-6 substituents R ^a as an optionally substituted divalent 5-to 14-membered aromatic heterocyclic residue , Where
R ^a is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -30 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-30 -alkyl, -O-COR ⁸ , -SC ₁ _-30 -alkyl, -NH ₂ , -NHR ⁸ , -NR ⁸ R ⁹ , -NH-COR ⁸ , -COOH , -COOR ⁸ , -CONH ₂ , -CONHR ⁸ , -CONR ⁸ R ⁹ , -CO-H, -COR ⁸ , C ₁ _-30 -alkyl optionally substituted with 1 to 6 substituents R ⁱ , the substituent optionally substituted with R ⁱ C ₂ _-30-alkenyl, one to six substituents R ^i, form a C ₂ _{-30-substituted-alkynyl,} one to six substituents R ^j optionally substituted C ₃ _-10 - selected from cycloalkenyl and 1-6 substituents group is optionally substituted by 1 R ^j consisting of a 3 to 14-membered aliphatic heterocyclic residue-cycloalkyl, 1-6 substituents R ^j optionally substituted C ₅ _-10 to , Where
R ⁸ and R ⁹ in each case independently of _one another are C ₁ _-30 -alkyl, C ₂ _-30 -alkenyl, C ₂ _-30 -alkynyl, C _3-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
R ⁱ is, independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 10, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 10, -NR}} 10 R 11, -NH-COR 10, -COOH ^{_{, -COOR 10, -CONH 2, -CONHR}} 10, -CONR 10 R 11, -CO-H, -COR 10, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,
R ^j is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 10, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 10, -NR}} 10 R 11, -NH-COR 10, -COOH ^{_{, -COOR 10, -CONH 2, -CONHR}} 10, -CONR 10 R 11, -CO-H, -COR 10, C 1 -10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein
R ¹⁰ and R ¹¹ are each independently at each occurrence C ₁ _-10 - alkyl, C ₂ _-10 - alkenyl, C _2-10 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - or selected from the group consisting of aryl and 1 is 5 to 14-membered aromatic heterocyclic residue,
or
G ¹ and G ² are independently of each other

, Where
Alkyl, - R ¹⁸ and R ¹⁹ are independently H or C ₁ _-30 from each other
L is a divalent 5- to 24-membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R ^b , optionally substituted with C ₆ _-24 -arylene or 1 to 6 substituents R ^b , wherein
R ^b is independently from each other in each case = _{O, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -30 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-30 -alkyl, -O-COR ¹² , -SC ₁ _-30 -alkyl, -NH ₂ , -NHR ¹² , -NR ¹² R ¹³ , -NH-COR ¹² , -COOH , -COOR ¹² , -CONH ₂ , -CONHR ¹² , -CONR ¹² R ¹³ , -CO-H, -COR ¹² , C ₁ _-30 -alkyl optionally substituted with 1 to 6 substituents R ^k , the substituent optionally substituted with R ^k C ₂ _-30 - alkenyl with 1 to 6 substituents R ^k optionally substituted C ₂ _-30 - alkynyl, 1-6 substituents R ^l optionally substituted with C ₃ _-10 - selected from cycloalkenyl and 1-6 substituents R ^l group consisting of optionally substituted 1 is a 3 to 14 membered aliphatic heterocyclic residue as - cycloalkyl, 1-6 substituents R ^l, optionally substituted C ₅ _-10 to , Where
R ¹² and R ¹³ are each independently at each occurrence C ₁ _-30 - alkyl, C ₂ _-30 - alkenyl, C ₂ _-30 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl C _1-6 -alkenyl, monovalent 3- to 14-membered aliphatic heterocyclic moieties, C _6-14 -aryl and monovalent 5- to 14-membered aromatic heterocyclic residues,
R ^k is independently = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 14, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 14, -NR}} 14 R 15, -NH-COR 14, -COOH ^{_{, -COOR 14, -CONH 2, -CONHR}} 14, -CONR 14 R 15, -CO-H, -COR 14, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,
R ^l is independently from each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 14, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 14, -NR}} 14 R 15, -NH-COR 14, -COOH ^{_{, -COOR 14, -CONH 2, -CONHR}} 14, -CONR 14 R 15, -CO-H, -COR 14, C 1 -10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein
R ¹⁴ and R ¹⁵ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - or selected from the group consisting of aryl and 1 is 5 to 14-membered aromatic heterocyclic residue,
or
L is

, Where
R ¹⁶ and R ^17, independently of each other H, C ₁ _-30 - alkyl, -CN or halogen,
q and s are independently of each other 0, 1, 2, 3, 4 or 5,
r is 0, 1 or 2,
n is an integer from 2 to 10,000.

The method of claim 1,
R ¹ is optionally substituted C ₁ _-30 by H or 1-6 substituents R ^c - alkyl, where
R ^c is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein
R ² and R ³ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
X is CR < ⁴ >, wherein
R ⁴ is optionally substituted C ₁ _-30 by H or 1-6 substituents R ^f - alkyl, where
R ^f is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein
R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
Wherein G ¹ , G ² , L, q, s, r and n are as defined in claim 1.

The method of claim 1,
R ¹ is C ₁ _-30 -alkyl optionally substituted with 1 to 6 substituents R ^c , wherein
R ^c is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 2, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 2, -NR}} 2 R 3, -NH-COR 2, -COOH ^{_{, -COOR 2, -CONH 2, -CONHR}} 2, -CONR 2 R 3, -CO-H, -COR 2, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C _{6 -14} -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein
R ² and R ³ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C _2-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
X is CR < ⁴ >, wherein
R ⁴ is optionally substituted C ₁ _-30 by H or 1-6 substituents R ^f - alkyl, where
R ^f is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 5, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 5, -NR}} 5 R 6, -NH-COR 5, -COOH ^{_{, -COOR 5, -CONH 2, -CONHR}} 5, -CONR 5 R 6, -CO-H, -COR 5, C 3-10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C _{6 -14} -aryl, and _monovalent 5- to 14-membered aromatic heterocyclic residues, wherein
R ⁵ and R ⁶ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
Wherein G ¹ , G ² , L, q, s, r and n are as defined in claim 1.

The method of claim 1,
Alkyl, - R ¹ is C ₁ _-30
X is CR < ⁴ >, wherein
R ⁴ is H,
Wherein G ¹ , G ² , L, q, s, r and n are as defined in claim 1.

5. The method according to any one of claims 1 to 4,
Wherein G < ¹ ^> and G < ² > are independently of each other monocyclic 2 optionally substituted with one to four substituents R &^lt; a > is a 5-8 membered aromatic heterocyclic residue,
R ^a is independently selected from = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -30 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-30 -alkyl, -O-COR ⁸ , -SC ₁ _-30 -alkyl, -NH ₂ , -NHR ⁸ , -NR ⁸ R ⁹ , -NH-COR ⁸ , -COOH , -COOR ⁸ , -CONH ₂ , -CONHR ⁸ , -CONR ⁸ R ⁹ , -CO-H, -COR ⁸ , C ₁ _-30 -alkyl optionally substituted with 1 to 6 substituents R ⁱ , the substituent optionally substituted with R ⁱ C ₂ _-30-alkenyl, one to six substituents R ^i, form a C ₂ _{-30-substituted-alkynyl,} one to six substituents R ^j optionally substituted C ₃ _-10 - selected from cycloalkenyl and 1-6 substituents group is optionally substituted by 1 R ^j consisting of a 3 to 14-membered aliphatic heterocyclic residue-cycloalkyl, 1-6 substituents R ^j optionally substituted C ₅ _-10 to , Where
R ⁸ and R ⁹ in each case independently of _one another are C ₁ _-30 -alkyl, C ₂ _-30 -alkenyl, C _2-30 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C _6-14 - is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue,
R ⁱ are independently from each other in each case = _{O, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 10, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 10, -NR}} 10 R 11, -NH-COR 10, -COOH ^{_{, -COOR 10, -CONH 2, -CONHR}} 10, -CONR 10 R 11, -CO-H, -COR 10, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _monovalent 5- to 14-membered aromatic heterocyclic residues,
R ^j is independently of each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, _{_{_{-O-CH 2 CH 2 OC 1}}} -10 - ^{_{alkyl, -O-COR 10, -SC 1}} -10 - _{^{alkyl, -NH 2, -NHR 10, -NR}} 10 R 11, -NH-COR 10, -COOH ^{_{, -COOR 10, -CONH 2, -CONHR}} 10, -CONR 10 R 11, -CO-H, -COR 10, C 1 -10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein
R ¹⁰ and R ¹¹ in each case independently of _one another are C ₁ _-10 -alkyl, C ₂ _-10 -alkenyl, C ₂ _-10 -alkynyl, C ₃ _-10 -cycloalkyl, C ₅ _-10 -cycloalkyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - which is selected from the group consisting of an aryl group and one 5- to 14-membered aromatic heterocyclic residue polymer.

The method according to any one of claims 1 to 5,
L is monocyclic 2 optionally substituted with 1 to 4 substituents R ^b is a 5- to 8-membered aromatic heterocyclic residue, wherein
R ^b is independently from each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -30 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-30 -alkyl, -O-COR ¹² , -SC ₁ _-30 -alkyl, -NH ₂ , -NHR ¹² , -NR ¹² R ¹³ , -NH-COR ¹² , -COOH ^{_{, -COOR 12, -CONH 2, -CONHR}} 12, -CONR 12 R 13, -CO-H, -COR 12, 1 to 6 substituents R ^k optionally substituted by C ₁ _-30-alkyl, 1 to 6 the substituent optionally substituted with R ^k C ₂ _-30 - alkenyl with 1 to 6 substituents R ^k optionally substituted C ₂ _-30 - alkynyl, 1-6 substituents R ^l optionally substituted with C ₃ _-10 - selected from cycloalkenyl and 1-6 substituents R ^l group consisting of optionally substituted 1 is a 3 to 14 membered aliphatic heterocyclic residue as - cycloalkyl, 1-6 substituents R ^l, optionally substituted C ₅ _-10 to Where
R ¹² and R ¹³ are each independently at each occurrence C ₁ _-30 - alkyl, C ₂ _-30 - alkenyl, C _2-30 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - is selected from the group consisting of aryl and 1 is 5 to 14-membered aromatic heterocyclic residue,
R ^k is independently = O each other at each _{occurrence, = C (CN) 2,} -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-10 -alkyl, -O-COR ¹⁴ , -SC ₁ _-10 -alkyl, -NH ₂ , -NHR ¹⁴ , -NR ¹⁴ R ¹⁵ , -NH-COR ¹⁴ , -COOH ^{_{, -COOR 14, -CONH 2, -CONHR}} 14, -CONR 14 R 15, -CO-H, -COR 14, C 3 -10 - cycloalkyl, a 3 to 14-membered aliphatic heterocyclic residue, C ₆ _-14 -aryl and _{monovalent 5-14} membered aromatic heterocyclic moiety;
R ^l is independently from each other in each case = O, = C (CN) 2, -OC 2 -6 - alkylene -O-, _{halogen, -CN, -NO 2, -OH,} C 1 -10 - alkoxy, -O-CH ₂ CH ₂ OC ₁ _-10 -alkyl, -O-COR ¹⁴ , -SC ₁ _-10 -alkyl, -NH ₂ , -NHR ¹⁴ , -NR ¹⁴ R ¹⁵ , -NH-COR ¹⁴ , -COOH ^{_{, -COOR 14, -CONH 2, -CONHR}} 14, -CONR 14 R 15, -CO-H, -COR 14, C 1 -10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl , C ₆ _-14 - 1 is aryl and is selected from the group consisting of 5- to 14-membered aromatic heterocyclic residue, wherein
R ¹⁴ and R ¹⁵ are each independently at each occurrence C ₁ _-10 - alkyl, C ₂ _-10 - alkenyl, C ₂ _-10 - alkynyl, C ₃ _-10 - cycloalkyl, C ₅ _-10 - cycloalkenyl alkenyl, a monovalent aliphatic 3-to 14-membered heterocyclic residue, C ₆ _-14 - or selected from the group consisting of aryl and 1 is 5 to 14-membered aromatic heterocyclic residue,
or
L

, Where
R ¹⁶ and R ¹⁷ is independently H or C ₁ _-30 each other -alkyl polymer.

7. The method according to any one of claims 1 to 6,
Wherein G < ¹ ^> and G < ² > are independently of each other monocyclic 2 optionally substituted with one to four substituents R &^lt; a > is a 5-8 membered aromatic heterocyclic residue,
R ^a is, independently of each other in each case C ₁ _-30 - alkyl polymer.

8. The method according to any one of claims 1 to 7,
L is monocyclic 2 is a 5- to 8-membered aromatic heterocyclic residue, wherein L may be optionally substituted with 1 to 4 substituents R ^b , wherein
Alkyl, - R ^b are independently C ₁ _-30 from each other in each case
or
L

, Where
R < ¹⁶ > and R < ¹⁷ > are both H.

The method according to any one of claims 1 to 8,
q and s are both 1,
r is 1,
and n is an integer of 5 to 10,000.

The polymer of claim 1 wherein the unit of formula 1 is a unit of formula 1a and / or formula 1′a.
<Formula 1a>

In this formula,
R ¹ , X, R ^a , L and n are as defined in claim 1.

11. The method of claim 10, wherein L is

ego,
R ¹ , X, R ^a and n are as defined in claim 1.

The method according to claim 10 or 11,
R ¹ and X are as defined in claim 3,
R < ^a > and n are as defined in claim 1.

The method according to claim 10 or 11,
R ¹ and X are as defined in claim 4,
R ^a is as defined in claim 7,
wherein n is as defined in claim 1.

The polymer according to any one of claims 1 to 13, wherein n is an integer of 5 to 5,000, more preferably 5 to 1,000, even more preferably 5 to 100, most preferably 10 to 100.

An electronic device comprising the polymer of claim 1 as a semiconductor material.

16. An electronic device according to claim 15, wherein the electronic device is an organic field effect transistor (OFET).

16. An electronic device according to claim 15, wherein the device is an organic photovoltaic device (OPV).

Use of the polymer of claim 1 as a semiconductor material.