A Rational Approach to Tetra‐Functional Photo‐Switches
A Rational Approach to Tetra‐Functional Photo‐Switches
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DOI：
10.1002/open.201900029
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发表时间：
2019-03
期刊：
影响因子：
2.3
通讯作者：
Philipp Niermeier;Jan-Hendrik Lamm;A. Mix;B. Neumann;H. Stammler;N. Mitzel
中科院分区：
文献类型：
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作者：
Philipp Niermeier;Jan-Hendrik Lamm;A. Mix;B. Neumann;H. Stammler;N. Mitzel
摘要以1，8-二氯-10(9H)-酮为起始原料，合成了含(CH2)n-键单元的α，ω-双(1，8-二氯-10-基)烷烃(n=1-4)。它被转化为在第10位具有烯丙基、溴甲基和丙叉基取代基的菲；它们在各种C-−C-键形成反应(加氢)中被转化，导致两个由α，ω-烷基柔性连接的菲单元。1，2-乙二基和1，3-丙二基连接的衍生物在1，8，1‘和8’位用乙炔基官能化，并且这些官能化由使用Me2NSnMe3的Me3Sn基团端化。通过紫外光诱导环化反应，得到了一系列9，10：9‘，10’-光环聚体。证明了它们的热循环反转和(重复)可切换性。以1，3‐Bis{1，8‐bis[(trimethylstannyl)ethynyl]anthracen‐10‐yl}propane作为光开关受体分子的模型化合物，通过核磁共振和剂量实验对其开环和闭合结构进行了表征。
Abstract α,ω‐Bis(1,8‐dichloroanthracen‐10‐yl)alkanes with (CH2)n‐linker units (n=1–4) were synthesized starting from 1,8‐dichloroanthracen‐10(9H)‐one. This was transformed into anthracenes with allyl, bromomethyl and propargyl substituents in position 10; these were converted in various C−C‐bond formation reactions (plus hydrogenation), leading to two anthracene units flexibly linked by α,ω‐alkandiyl groups. 1,2‐Ethandiyl‐ and 1,3‐propandiyl‐linked derivatives were functionalized with ethynyl groups in positions 1, 8, 1’ and 8’, and these terminally functionalized by Me3Sn groups using Me2NSnMe3. All linked bisanthracenes were subjected to UV light induced cyclomerization and a series of 9,10 : 9’,10’‐photo‐cyclomers were obtained. Their thermal cycloreversion and (repeated) switchability was demonstrated. 1,3‐Bis{1,8‐bis[(trimethylstannyl)ethynyl]anthracen‐10‐yl}propane served as model compound for photo‐switchable acceptor molecules and its open and closed forms were characterized by NMR and DOSY experiments.