Redox-Modulated Stepwise Photochromism in a Ruthenium Complex with Dual Dithienylethene-Acetylides
Redox-Modulated Stepwise Photochromism in a Ruthenium Complex with Dual Dithienylethene-Acetylides
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具有双二噻吩乙烯-乙酰化物的钌配合物中氧化还原调节的逐步光致变色
DOI：
10.1021/ja3076204
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发表时间：
2012-09-26
影响因子：
15
通讯作者：
Chen, Zhong-Ning
中科院分区：
文献类型：
--
作者：
Li, Bin;Wang, Jin-Yun;Chen, Zhong-Ning
Achieving stepwise photochromism in a combined molecule to access all of the possible ring-open/closed isomers is a Challenge due to facile energy transfer from ring-open dithienylethene (DTE) to an adjacent ring-closed moiety that prohibits further photocyclization. The preparation, characterization, and photochromic properties of a bis(sigma-acetylide) bonded ruthenium(II) complex 2oo and its oxidized form 2oo(+) with two identical DTE-acetylides (Llo) are described. Stepwise and dual photochromic reactions are successfully achieved in both 2oo and 2oo(+), in which the ring-closing absorption band of 2oo(+) shows an obvious blue-shift relative to 2oo. It is demonstrated that stepwise photochromic reactions 2oo -> 2co -> 2cc are more facile than 2oo(+)-> 2co(+)-> 2cc(+). The lower electronic density at the reactive carbon atoms upon oxidation of Ru(II) to Ru(III) causes photocyclization to have more difficulty proceeding in oxidized species 2oo(+)/2co(+). Upon dual ring-closure, 2cc/2cc(+) exhibits significant electronic interaction between two identical ring-closed DTE units across trans-Ru(dppe)(2) spacer. The interconversion processes among six states are unambiguously demonstrated by NMR, UV-vis-NIR, and IR spectroscopic, and electrochemical and computational studies.
