螺双硅[7]螺旋烯的合成与性质：最低未占分子轨道螺共轭
Synthesis and Properties of Spiro-double Sila[7]helicene: The LUMO Spiro-conjugation.
作者信息
Terada Nozomi, Uematsu Keisuke, Higuchi Ryota, Tokimaru Yuki, Sato Yosuke, Nakano Koji, Nozaki Kyoko
机构信息
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo, 184-8588, Japan.
出版信息
Chemistry. 2021 Jun 25;27(36):9342-9349. doi: 10.1002/chem.202100385. Epub 2021 May 19.
A double helicene with a spiro-Si linker (4) was synthesized by four successive nucleophilic substitutions on SiCl . Its (P,P), (M,M) and (P,M) isomers were isolated and characterized by single crystal X-ray analysis. Due to the central spirosilabi[fluorene] moiety, the two helicene units in 4 are symmetrically and nearly perpendicularly arranged. (P,P)-4 and (M,M)-4 exhibit unique optical properties attributable to the LUMO spiro-conjugation between the two sila[7]helicene units.
通过在SiCl₄上进行四次连续的亲核取代反应合成了一种带有螺硅连接基的双螺旋烯（4）。分离出了其（P，P）、（M，M）和（P，M）异构体，并通过单晶X射线分析对其进行了表征。由于中心螺硅双芴部分，4中的两个螺旋烯单元对称且几乎垂直排列。（P，P）-4和（M，M）-4表现出独特的光学性质，这归因于两个硅[7]螺旋烯单元之间的最低未占分子轨道（LUMO）螺共轭。
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