Synthesis of Donor-Acceptor Polymers Containing Thiazolo[5,4-d]thiazole Units via Palladium-Catalyzed Direct Arylation Polymerization
Synthesis of Donor-Acceptor Polymers Containing Thiazolo[5,4-d]thiazole Units via Palladium-Catalyzed Direct Arylation Polymerization
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DOI：
10.1021/acs.macromol.5b01822
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发表时间：
2015-11-24
期刊：
影响因子：
5.5
通讯作者：
Ozawa, Fumiyuki
中科院分区：
文献类型：
--
作者：
Wakioka, Masayuki;Ishiki, Satoru;Ozawa, Fumiyuki
本文报道了通过钯催化的直接芳基化聚合（DArP）合成含噻唑单元的交替给体-受体共聚物（DA聚合物），该聚合物最近成为常规交叉偶联缩聚的可行替代物。虽然基于噻唑的C-H单体如苯并二噻唑和噻唑并噻唑对DArP的反应性差，但在2，5-位用5-溴噻吩基和噻吩基封端的噻唑并噻唑（TzTz）、2，5-双[5-溴-3-（三氟甲基）噻吩基]噻吩基和噻吩基封端的噻唑并噻唑（TzTz）对DArP的反应性差。（2-辛基十二烷基）噻吩-2-基]-噻唑并[5，4-d]噻唑（1-Br）和2，5-双[3-（三氟甲基）噻吩-2-基]-噻唑并[5，4-d]噻唑（2-辛基十二碳噻吩-2-基）噻唑并[5，4-d]噻唑（1-H）分别与C-H和C-Br单体成功反应。在Pd-2（dba）（3）和P（2-MeOC 6 H4）（3）（L1）作为催化剂前体和新戊酸和Cs2 CO 3作为添加剂的存在下，在100 ℃下在THF中进行反应，以几乎定量的产率得到具有高分子量（M-n高达88 100）和良好溶解性的含TzTz的DA聚合物。所得聚合物的高温NMR分析揭示了含有少量同偶缺陷的良好控制的结构。
This paper reports the synthesis of alternating donor-acceptor copolymers (DA polymers) containing thiazole units via palladium-catalyzed direct arylation polymerization (DArP), which has recently emerged as a viable alternative to conventional cross-coupling polycondensations. While thiazole-based C-H monomers such as benzodithiazole and thiazolothiazole are poorly reactive toward DArP, thiazolothiazoles (TzTz) capped with 5-bromothienyl and thienyl groups at the 2,5-positions, 2,5-bis[5-bromo-3-(2-octyldodecyl)thiophene-2-yl]-thiazolo [5,4-d]thiazole (1-Br) and 2,5-bis[3-(2-octyldodecypthiophene2-yl] thiazolo [5,4-d] thiazole (1-H), successfully react with C-H and C-Br monomers, respectively. The reactions proceed in THF at 100 degrees C in the presence of Pd-2(dba)(3) and P(2-MeOC6H4)(3) (L1) as catalyst precursors and pivalic acid and Cs2CO3 as additives to afford TzTz-containing DA polymers with high molecular weight (M-n up to 88 100) and good solubility in almost quantitative yields. A high-temperature NMR analysis of the resulting polymers reveals well-controlled structures containing a small amount of homocoupling defects.