Steric Effects of the Initiator Substituent Position on the Externally Initiated Polymerization of 2-Bromo-5-iodo-3-hexylthiophene

被引：58

作者：

Doubina, Natalia ^{[2
]}

Paniagua, Sergio A. ^{[3
]}

Soldatova, Alexandra V. ^{[2
]}

Jen, Alex K. Y. ^{[1
,2
]}

Marder, Seth R. ^{[3
]}

Luscombe, Christine K. ^{[1
]}

机构：

[1] Univ Washington, Dept Mat Sci & Engn, Seattle, WA 98195 USA

[2] Univ Washington, Dept Chem, Seattle, WA 98195 USA

[3] Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA

来源：

MACROMOLECULES | 2011年 / 44卷 / 03期

基金：

美国国家科学基金会;

关键词：

CATALYST-TRANSFER POLYCONDENSATION; CHAIN-GROWTH POLYMERIZATION; CONTROLLED MOLECULAR-WEIGHT; OXIDATIVE ADDITION; THIOPHENE COORDINATION; BLOCK-COPOLYMERS; PHOSPHINE LIGAND; COMPLEXES; NICKEL; SURFACE;

D O I：

10.1021/ma1024494

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Externally initiated polymerization of 2-bromo-3-hexyl-5-iodothiophene was attempted from four aryl and thiophene based small molecule initiators functionalized with a phosphonate moiety. Initiated poly(3-hexylthiophene) product was obtained in various yields depending on the nature of the initiating molecule. Reaction intermediates for the oxidative addition and the ligand exchange steps were analyzed utilizing both experimental and theoretical methods. It was observed that an ortho substituent plays a crucial role in the outcome of the polymerization mechanism and that aryl based initiators are generally more stable than thiophene based initiators. Density functional theory (DFT) calculations revealed the importance of the steric effects on the success of the externally initiated chain growth polymerization mechanism.

引用

页码：512 / 520

页数：9

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