Chiral Nanostructures from Helical Copolymer-Metal Complexes: Tunable Cation-π Interactions and Sergeants and Soldiers Effect

被引：46

作者：

Arias, Sandra ^{[1
]}

Bergueiro, Julian ^{[1
]}

Freire, Felix ^{[1
]}

Quinoa, Emilio ^{[1
]}

Riguera, Ricardo ^{[1
]}

机构：

[1] Univ Santiago de Compostela, Ctr Res Biol Chem & Mol Mat CIQUS, Santiago De Compostela 15782, Spain

来源：

SMALL | 2016年 / 12卷 / 02期

关键词：

POLY(PHENYLACETYLENE) DERIVATIVES BEARING; CINCHONA ALKALOID PENDANTS; SOLID-STATE; MACROMOLECULAR HELICITY; 2-DIMENSIONAL CRYSTAL; DILUTE-SOLUTION; LIQUID-CRYSTAL; AMPLIFICATION; POLYMERS; POLYACETYLENE;

D O I：

10.1002/smll.201502276

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Poly(phenylacetylene) (PPA) copolymers containing (R)- or (S)-MPA as minor chiral pendant can be forced to selectively adopt the right-o left-handed helix, in the presence of small amounts of Na+ or Ag+ ("Sergeants and Soldiers Effect") by addition of a donor cosolvent. The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a perfect on/off tuning of the helicity of the copolymer. When the amount of the donor cosolvent is low, the metal ion complex is stabilized by a cation-pi interaction, which is selectively cleaved when the amount of cosolvent is higher. Macroscopically chiral nanospheres and nanotubes composed by helical copolymers with P or M helical sense are also described. Our results demonstrate that it is possible to obtain the two enantiomeric helical structures (P and M helicities) and the corresponding nanospheres and nanotubes from a single helical copolymer, by controlled activation/deactivation of the Sergeant and Soldiers Effect with a donor cosolvent.

引用

页码：238 / 244

页数：7

共 69 条

[1] Synthesis and chiral recognition ability of helical polyacetylenes bearing helicene pendants [J].