Coordination chemistry strategies for dynamic helicates: time-programmable chirality switching with labile and inert metal helicates

被引:171
作者
Miyake, Hiroyuki [1 ]
Tsukube, Hiroshi [1 ,2 ]
机构
[1] Osaka City Univ, Dept Chem, Grad Sch Sci, Sumiyoshi Ku, Osaka 5588585, Japan
[2] Japan Sci & Technol Agcy JST, CREST, Chiyoda Ku, Tokyo 1020076, Japan
基金
日本学术振兴会; 日本科学技术振兴机构;
关键词
HELICITY INVERSION; LANTHANIDE(III) COMPLEXES; MOLECULAR SWITCH; INFORMATION; DNA; ENANTIOPURE; RECOGNITION; TRANSITION; HANDEDNESS; POLYMERS;
D O I
10.1039/c2cs35192g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
'Chirality switching' is one of the most important chemical processes controlling many biological systems. DNAs and proteins often work as time-programmed functional helices, in which specific external stimuli alter the helical direction and tune the time scale of subsequent events. Although a variety of organic foldamers and their hybrids with natural helices have been developed, we highlight coordination chemistry strategies for development of structurally and functionally defined metal helicates. These metal helicates have characteristic coordination geometries, redox reactivities and spectroscopic/magnetic properties as well as complex chiralities. Several kinds of inert metal helicates maintain rigid helical structures and their stereoisomers are separable by optical resolution techniques, while labile metal helicates offer dynamic inversion of their helical structures via non-covalent interactions with external chemical signals. The latter particularly have dynamically ordered helical structures, which are controlled by the combinations of metal centres and chiral ligands. They further function as time-programmable switches of chirality-derived dynamic rotations, translations, stretching and shape flipping, which are useful applications in nanoscience and related technology.
引用
收藏
页码:6977 / 6991
页数:15
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