Optically active polysilanes. Ten years of progress and new polymer twist for nanoscience and nanotechnology

被引:143
作者
Fujiki, M
Koe, JR
Terao, K
Sato, T
Teramoto, A
Watanabe, J
机构
[1] JST, CREST, Kawaguchi, Saitama 3320012, Japan
[2] Nara Inst Sci & Technol, Adv Polymer Sci Lab, Grad Sch Mat Sci, Nara 6300101, Japan
[3] Int Christian Univ, Dept Chem, Tokyo 1818585, Japan
[4] Gunma Univ, Dept Biol & Chem Engn, Kiryu, Gumma 3768515, Japan
[5] Osaka Univ, Dept Macromol Sci, Toyonaka, Osaka 5600043, Japan
[6] Ritsumeikan Univ, Res Org Sci & Engn, Shiga 5258577, Japan
[7] Tokyo Inst Technol, Dept Organ & Polymer Mat, Tokyo 1528552, Japan
关键词
polysilane; optically active; helix; chiral; circular dichroism; fluorescence; conformation;
D O I
10.1295/polymj.35.297
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
In the family of optically active synthetic polymers, optically active polysilanes, which comprise a helical main chain of silicon-silicon single bonds and chiral and/or achiral side groups, exhibit unique absorption, circular dichroism, and fluorescence spectra around 300-400nm due to sigma-conjugation. Since the first brief report of optically active polysilane synthesis in 1992, the field has now widened to include various homo- and copolymers of optically active poly(dialkylsilane)s, poly(dialkoxysilane)s, poly [alkyl(aryl)silane] s, and poly(diarylsilane)s. This review comprehensively covers work on (i) the relationship between side chain structure, (ii) local structure-global shape relationship, (iii) (chir)optical properties, (iv) (semi)quantitative population analysis of right- and left-handed helices based on Kuhn's dissymmetry ratio, (v) several helical cooperativity effects, (vi) molecular imaging, (vii) inversion of screw-sense, (viii) chiroptical switch and memory, (ix) transfer and amplification of molecular chirality to aggregates, (x) cholesteric liquid crystallinity, (xi) helical supramolecular structures, and (xii) latent helicity, as consequences of side group internal interactions and other external stimuli. Such knowledge and understanding may stimulate optically active polymer research in the realm of nanomaterial science and nanotechnology at the sub-nm level as well as traditional polymer science, and may advance these polymers to new functional nanomaterials and thence to the realization of nanodevices in the future.
引用
收藏
页码:297 / 344
页数:48
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