Stille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution

doi:10.1039/d2sc06702a

	Stille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution
	Zhang, Zhikai; Zhang, Boyang; Han, Xue; Chen, Hongyi; Xue, Cece; Peng, Min; Ma, Guijun; Ren, Yi
	2023
发表期刊	CHEMICAL SCIENCE (IF:7.6[JCR-2023],8.0[5-Year])
ISSN	2041-6520
EISSN	2041-6539
卷号	14 期号:11 页码:268-320
DOI	10.1039/d2sc06702a
摘要	Recently, exploring new type polymerization protocols has been a major driving force in advancing organic polymers into highly functional materials. Herein we report a new polycondensation protocol to implant the phosphorus (P) atom in the main backbone of crosslinked polythiophenes. The polycondensation harnesses a Stille phosphorus-carbon (P-C) coupling reaction between phosphorus halides and aryl stannanes that has not been reported previously. Mechanistic studies uncovered that the P-electrophile makes the reactivity of a catalytic Pd-center highly sensitive towards the chemical structures of aryl stannanes, which is distinct from the typical Stille carbon-carbon coupling reaction. The efficient P-C polycondensation afforded a series of P-crosslinked polythiophenes (PC-PTs). Leveraging on the direct P-crosslinking polymerization, solid-state 31P NMR studies revealed highly uniform crosslinking environments. Efficient post-polymerization P-chemistry was also applied to the PC-PTs, which readily yielded the polymers with various P-environments. As a proof of concept, new PC-PTs were applied as the photocatalysts for H2 evolution under visible light irradiation. PC-PTs with an ionic P(Me)-center exhibit a H2 evolution rate up to 2050 μmol h−1 g−1, which is much higher than those of PC-PTs with a P(O)-center (900 μmol h−1 g−1) and P(iii)-center (155 μmol h−1 g−1). For the first time, the studies reveal that regulating P-center environments can be an effective strategy for fine tuning the photocatalytic H2 evolution performance of organic polymers. © 2023 The Royal Society of Chemistry.
关键词	Covalent bonds Crosslinking Functional materials Hydrogen Organic polymers Polycondensation Thiophene Coupling reaction Crosslinked Driving forces Electrophiles H 2 evolution Mechanistic studies Phosphorus halides Photocatalytic hydrogen evolution Polycondensations Stannane
URL	查看原文
收录类别	EI ; SCOPUS
语种	英语
出版者	Royal Society of Chemistry
EI入藏号	20231013669013
EI主题词	Carbon
EI分类号	801.4 Physical Chemistry ; 802.2 Chemical Reactions ; 804 Chemical Products Generally ; 804.1 Organic Compounds ; 815.1.1 Organic Polymers ; 815.2 Polymerization ; 951 Materials Science
原始文献类型	Article in Press
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/284254
专题	物质科学与技术学院_硕士生物质科学与技术学院_PI研究组_马贵军组物质科学与技术学院_公共科研平台_分析测试平台物质科学与技术学院_PI研究组_任毅组物质科学与技术学院_博士生
通讯作者	Ma, Guijun; Ren, Yi
作者单位	School of Physical Science and Technology, ShanghaiTech University, Shanghai; 201210, China
第一作者单位	物质科学与技术学院
通讯作者单位	物质科学与技术学院
第一作者的第一单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Zhang, Zhikai,Zhang, Boyang,Han, Xue,et al. Stille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution[J]. CHEMICAL SCIENCE,2023,14(11):268-320.
APA	Zhang, Zhikai.,Zhang, Boyang.,Han, Xue.,Chen, Hongyi.,Xue, Cece.,...&Ren, Yi.(2023).Stille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution.CHEMICAL SCIENCE,14(11),268-320.
MLA	Zhang, Zhikai,et al."Stille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution".CHEMICAL SCIENCE 14.11(2023):268-320.