Creating a Vision for Photochromic and Chiral Helicenoid Diarylethenes

创造光致变色和手性螺烯二芳基乙烯的愿景

• 批准号: 17550047
• 负责人: YOKOYAMA Yayoi
• 金额: $ 2.44万
• 依托单位: Tokyo Kasei Gakuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17550047/
• 关键词: photochromism; helicene; diarylethene; diastereoselectivity; benzothiophene; perfluorocyclopentene; repulsion; methoxyl; 光学活性; ビナフトール; フォトクロミズム; へリックス; 旋光度; 量子収率; ヘリセン; ジアステレオ選択的; アリリックストレイン; 光閉環反応

Helicenes are known to show large specific optical rotation. In order to induce a large change in optical rotation, a diastereoselective photochromic reaction should take place. We chose to induce a diastereoselective photochromic reaction with a simple chiral auxiliary attached to the ring-closing hexatriene moiety. Then, we synthesized six chiral helicenoid diarylethenes having the aromatic group connected to perfluorocyclipentene at C-3 or C-2. We examined the photochemical behaviors of these six molecules, especially about the diastereoselectivity in photochromism. In the course of these investigations, we could gain the useful inspection about the relation between the diastereoselectivity and the substitution groups (methoxyl group and methoxymethoxyl group) in diarylethenes to obtain large optical rotation changes in photochromism. That is, we found the steric and electronic repulsion between two substitution groups and the electronic repulsion between the methoxyl group and benzothiophen moiety in these molecules were important.

已知螺旋烯表现出大的比旋光度。为了引起旋光度的大变化，应发生非对映选择性光致变色反应。我们选择用连接到闭环己三烯部分的简单手性助剂来诱导非对映选择性光致变色反应。然后，我们合成了六种手性螺烯二芳基乙烯，其芳族基团在C-3或C-2处连接到全氟环戊烯。我们研究了这六个分子的光化学行为，特别是光致变色中的非对映选择性。在这些研究过程中，我们可以对二芳基乙烯中的非对映选择性和取代基（甲氧基和甲氧基甲氧基）之间的关系进行有用的检查，以获得光致变色的大旋光度变化。也就是说，我们发现这些分子中两个取代基之间的空间和电子排斥以及甲氧基和苯并噻吩部分之间的电子排斥很重要。

项目成果

Mol. Cryst. Liq. Cryst, 1, 3-Bisarylbutadienes : Novel Thermally Irreversible

摩尔。

• 发表时间: 2005
• 作者: Yasushi; Yokoyama
• 通讯作者: Yokoyama

Chiral Helicenoid Diarylethene with Highly Diastereoselective Photocyclization

具有高度非对映选择性光环化的手性螺烯二芳基乙烯

• 发表时间: 2007
• 作者: Yutaka Tani

Novel Thermally Reversible Photochromic Compounds : Dihydrobenzothiophene and Dihydronaphthalene

新型热可逆光致变色化合物：二氢苯并噻吩和二氢萘

• 发表时间: 2005
• 作者: Yasushi; Yokoyama
• 通讯作者: Yokoyama

Novel Thermally Reversible Photochromic Compounds:Dihydrobenzothiophene and Dihydronaphthalene

新型热可逆光致变色化合物：二氢苯并噻吩和二氢萘

• 发表时间: 2005
• 作者: Yasushi Yokoyama

1,3-Bisarylbutadienes:Novel Thermally Irreversible Photochromic System

1,3-双芳基丁二烯：新型热不可逆光致变色系统

• 发表时间: 2005
• 作者: Yasushi Yokoyama