Synthesis of homo polymers and block copolymers of chiral/achiral phenylacetylene derivatives. Spectroscopic and molecular modeling study on solvent-dependent predominance of helical sense

被引：3

作者：

Goto, Masahide ^{[1
]}

Mino, Shota ^{[1
]}

Sogawa, Hiromitsu ^{[1
]}

Sanda, Fumio ^{[1
,2
]}

机构：

[1] Kansai Univ, Fac Chem Mat & Bioengn, Dept Chem & Mat Engn, Osaka, Japan

[2] Kansai Univ, Fac Chem Mat & Bioengn, Dept Chem & Mat Engn, 3-3-35 Yamate cho, Suita, Osaka 5648680, Japan

来源：

JOURNAL OF POLYMER SCIENCE | 2023年 / 61卷 / 13期

关键词：

helical polymer; MD simulation; polyacetylene; pi-conjugated polymer; CIS-TRANS ISOMERIZATION; LIVING POLYMERIZATION; CHIRALITY; AMPLIFICATION; CATALYST; CHAIN; POLY(N-PROPARGYLAMIDES); COMPETITION; PARAMETERS;

D O I：

10.1002/pol.20220765

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

A chiral acetylene monomer, (S)-4-(2-butoxy)phenylacetylene [(S)-1] and an achiral acetylene monomer, 4-propoxyphenylacetylene (2) were block copolymerized using [(nbd)Rh{C(Ph)=CPh2}(PPh3)]/PPh3 as a catalyst to obtain chiral-first/achiral-second and achiral-first/chiral-second block copolymers, poly[(S)-1]-block-poly(2) and poly(2)-block-poly[(S)-1]. The block copolymers exhibited circular dichroism (CD) signals in THF attributable to helical conformation with predominantly one-handed screw sense originating from the poly[(S)-1] block. In CHCl3, the block copolymers exhibited CD signals with signs reversed from those in THF. The conformational stability of the copolymers was dependent on the composition of (S)-1 units, regardless of the feed order of the chiral and achiral monomers. The solvent-dependent predominance of helical sense was confirmed by the molecular dynamics (MD) simulations of poly[(S)-1] 32-mer models.

引用

页码：1270 / 1278

页数：9