Azo- and quinone-conjugated redox complexes -: photo- and proton-coupled intramolecular reactions based on d-π interaction
Azo- and quinone-conjugated redox complexes -: photo- and proton-coupled intramolecular reactions based on d-π interaction
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DOI：
10.1016/s0010-8545(01)00421-0
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发表时间：
2002-03-01
影响因子：
20.6
通讯作者：
Nishihara, H
中科院分区：
文献类型：
--
作者：
Kurihara, M;Nishihara, H
本文描述了偶氮和醌共轭金属配合物基于d-pi电子相互作用的新型光-质子耦合行为。偶氮苯桥联双三联吡啶配合物的光异构化量子产率显著地依赖于金属、抗衡离子和溶剂的性质。偶氮二茂铁的反式-顺式异构化不仅通过π-π * 跃迁带的光激发进行，而且通过MLCT（d-pi* 跃迁）带的光激发进行。的二茂铁部分的氧化发生在0.3 V以下的正电位，和二茂铁部分之间的电子相互作用是显着较弱的顺式-偶氮二茂铁比反式-偶氮二茂铁。在亚乙烯基桥接的二茂铁-对苯二酚络合物中，二茂铁基位点的氧化促进羟基和亚乙烯基质子的消除，随后通过分子内电子转移形成丙二烯和醌结构。1-二茂铁基乙炔基蒽醌中蒽醌部分的羰基质子化引起分子内电子转移，导致η（6）-富烯-累积多烯Fe（II）络合物的新结构变化。(C)2002 Elsevier Science B. V.保留所有权利。
Novel photo- and proton-coupled behavior of azo- and quinone-conjugated metal complexes based on the d-pi electronic interaction is described. The quantum yield for photoisomerization of azobenzene-bridged bis(terpyridine) complexes significantly depends on the nature of the metal, counterions, and solvents. The trans-to-cis isomerization of azoferrocene proceeds not only by the photoexcitation of the pi-pi* transition band but also by the photoexcitation of the MLCT (d-pi* transition) band. The oxidation of the ferrocene moieties occurs at 0.3 V less positive potential, and the electronic interaction between the ferrocene moieties is significantly weaker in cis-azoferrocene than in trans-azoferrocene. In a vinylene-bridged ferrocene-hydroquinone complex, the oxidation of the ferrocenyl site promotes the elimination of the hydroxyl and the vinylene protons followed by intramolecular electron transfer to form an allene and a quinonoid structure. The protonation to carbonyl groups of the anthraquinone moiety in 1-ferrocenylethynylanthraquinone causes intramolecular electron transfer leading to a novel structural change into a eta(6)-fulvene-cumulene Fe(II) complex. (C) 2002 Elsevier Science B.V. All rights reserved.