Platinum diimine complexes: towards a molecular photochemical device
Platinum diimine complexes: towards a molecular photochemical device
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DOI：
10.1016/s0010-8545(00)00254-x
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发表时间：
2000-10-01
影响因子：
20.6
通讯作者：
Eisenberg, R
中科院分区：
文献类型：
--
作者：
Hissler, M;McGarrah, JE;Eisenberg, R
具有通式为PtX2(二亚胺)的配合物，其中X-2=二硫代，双(乙酰)和二亚胺=联吡啶，邻菲咯啉及其衍生物，已被研究在光能到化学能的转化中作为生色团的潜在用途。这些络合物，就像类似的X=CN体系一样，在流体溶液中发光。前人对二硫酸盐衍生物的研究表明，它们具有电荷转移激发态，包括一个混合的金属-二硫代硫酸盐供体轨道和一个pi*(二亚胺)受体功能，其激发态性质包括发射能量、寿命和氧化还原电势，这些性质可以通过配体的变化来调节。双乙酰配合物在流体溶液中发光很强，其激发态为MLCT，与先前的理论一致，两组双亚胺配合物都表现出自猝灭现象，而对于铂(Phen)(CCPh)(2)，观察到微弱的准分子发射。通过交叉猝灭实验对猝灭机理进行了探讨，认为它涉及到铂与铂之间的相互作用。目前正在努力将PtX2(二亚胺)发色团用于二联体和三联体中，目标是构建用于光到化学能量转换的分子光化学装置。目前正在利用钯催化的偶联反应和羰基缩合反应合成新的配体桥，从而使铂的二亚胺发色团与给体或还原猝灭剂和受体连接起来。(C)2000 Elsevier Science S.A.保留所有权利。
Complexes having the general formula PtX2(diimine) where X-2 = dithiolate, bis(acetylide) and diimine = bipyridine, phenanthroline and derivatives have been investigated for potential use as chromophores in the conversion of light-to-chemical energy. These complexes, like the analogous X = CN systems, are luminescent in fluid solution. Previous studies of the dithiolate derivatives reveal that they possess a charge transfer excited state involving a mixed metal-dithiolate donor orbital and a pi*(diimine) acceptor function with excited state properties including emission energies, lifetimes and redox potentials that are tunable by ligand variation. The bis(acetylide) complexes are brightly luminescent in fluid solution, and their excited state is shown to be MLCT in character, consistent with an earlier proposal, Both sets of diimine complexes show evidence of self-quenching, and for Pt(phen)(CCPh)(2), weak excimer emission is observed. The mechanism of quenching has been probed through cross-quenching experiments and is thought to involve Pt...Pt interactions. Efforts are now focussing on the use of the PtX2(diimine) chromophores in dyads and triads with the goal of constructing a molecular photochemical device for light-to-chemical energy conversion. Connection of the Pt diimine chromophores to both a donor or reductive quencher and an acceptor is envisioned through new ligand bridges currently being synthesized using Pd-catalyzed coupling reactions and carbonyl condensations. (C) 2000 Elsevier Science S.A. All rights reserved.