Photoredox Reactions of Mixed-Valence Compounds Induced by Intervalence Excitation
Photoredox Reactions of Mixed-Valence Compounds Induced by Intervalence Excitation
复制标题
间隔激发诱导的混合价化合物的光氧化还原反应
DOI：
10.1016/0010-8545(85)80048-5
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发表时间：
1985
影响因子：
20.6
通讯作者：
H. Kunkely
中科院分区：
文献类型：
--
作者：
A. Vogler;A. Osman;H. Kunkely
研究表明，多种混合价体系在水溶液中通过价间（IT）带吸收光时具有光活性。IT激发导致电子从还原金属中心转移到氧化金属中心。Co（III）、Ru（III）、Cr（III）和Os（III）配合物作为电子受体，[Fe（CN）6]4-、[Ru（CN）6]4-和[Os（CN）6]4-作为电子供体。研究了内球系统和外球系统。在双核配合物中，内球IT相互作用是通过桥连氰化物配体介导的。外层IT系统是由作为阳离子的氧化性络合物和还原性六氰根阴离子的离子对形成的。光诱导的金属到金属的电子转移之后，产生稳定的光产物的二次过程。
A variety of mixed-valence systems were shown to be photoactive in aqueous solution upon light absorption by the intervalence (IT) band. IT excitation leads to an electron transfer from a reducing to an oxidizing metal center. Co(III), Ru(III), Cr(III), and Os(III) complexes were used as electron acceptors while [Fe(CN)6]4-, [Ru(CN)6]4-, and [Os(CN)6]4-servede as electron donors. Inner- as well as outer-sphere systems were studied. The inner-sphere IT interaction was mediated by bridging cyanide ligands in binuclear complexes. Outer-sphere IT systems were formed by ion pairs of the oxidizing complexes as cations and the reducing hexacyanide anions. Light-induced metal to metal electron transfer was followed by secondary processes which yields stable photoproducts.