有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
総説および総合論文
電子供与性[n]デンドラレン類の合成,構造と性質
長谷川 真士渡邊 美穂御崎 洋二
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ジャーナル 認証あり

2013 年 71 巻 12 号 p. 1268-1281

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Dendralenes, acyclic cross-conjugated polyenes having a nonplanar structure, containing 1,3-dithiole (DT) rings are of considerable interest as novel multi-stage redox systems for potential application to electrical conducting, magnetic, electrochromic, and nonlinear optical materials. In the present review, we focus on the electronic structures of DT[n]dendralenes and their π-extended compounds in which phenylene, thienylene, furylene, or tetrathiapenthalene (TTP) moieties are inserted. DT[n]dendralenes (n=3 and 4) employ a non-planar structure due to the steric effect, and cyclic voltammetry (CV) suggested multi-redox behavior of extended vinylogues. Their electronic structure and conjugation pathway in cationic states are strongly affected by the aromaticity of the inserted aryl groups. As for dication of DT[4]dendralenes with two thiophene spacers, the electronic structures depend on their substituents. In the cationic states of DT[5]dendralenes with two thiophene spacers, the positive charges are mainly located on the outer TTF moieties. On the other hand, cationic species of DT[3]dendralene having two TTP moieties, the positive charges are distributed mainly in the outer branching vinylogues.
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