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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Investigation of Electron Delocalization and Ultrafast Studies of Ru~(II)/Os~(II) Dyads with Ethynyl/Butadiynyl-Bridged Polyphosphines
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Investigation of Electron Delocalization and Ultrafast Studies of Ru~(II)/Os~(II) Dyads with Ethynyl/Butadiynyl-Bridged Polyphosphines

机译：乙炔基/丁二炔基桥接的多膦对Ru〜（II）/ Os〜（II）二元电子的电子离域和超快研究

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摘要

The redox characteristics, electronic absorption, steady-state emission, nanosecond laser flash photolysis, and a femtosecond laser spectroscopic study have been carried out for a series of monomeric, homobimetallic, and heterobimetallic complexes with M(bpy)_2Cl-based moieties (M = Ru~(II) and Os~(II)) and ethynyl- and butadiynyl-bridged polyphosphines, namely Ph_2PC(ident to)CPPh_2 (C_2P_2) and Ph_2PC(ident to)CC(ident to)CPPh_2 (C_4P_2). These complexes were synthesized by reactions of the spacers with cis-M(bpy)_2Cl_2 or by coupling reaction between two [Cl(bpy)_2M(Ph_2PC(ident to)CH)](PF_6) (M = Ru~(II), Os~(II)) molecules. Electronic communication through polyphosphine/polyyne spacers is found to decrease upon increase of the carbon chain length, and the comproportionation constant K_c was calculated as 14-18 for species with C_2P_2 and ca. 4 for the ones with C_4P_2. In addition, fast intramolecular energy transfer from the Ri~(II)-based donor to the Os~(II)-based acceptor, with rate constant of (2.4-2.5) X 10~9 s~(-1), occurs within heterobimetallic complexes via a Dexter-type mechanism and an attenuation factor (#beta#) of 0.02 A~(-1).
机译：已经对一系列具有M（bpy）_2Cl基部分的单体，同双金属和杂双金属配合物进行了氧化还原特性，电子吸收，稳态发射，纳秒激光闪光光解和飞秒激光光谱研究（M = Ru〜（II）和Os〜（II））以及乙炔基和丁二炔基桥联的多膦，即Ph_2PC（与CPPh_2（C_2P_2）和Ph_2PC（与CCCP）（CP_4P_2）相同）。这些配合物是通过间隔基与顺式M（bpy）_2Cl_2的反应或两个[Cl（bpy）_2M（Ph_2PC（与CH相同的CH）]] [PF_6）（M = Ru〜（II）， Os〜（II））分子。发现通过多膦/聚炔间隔基的电子通讯随着碳链长度的增加而减少，对于具有C_2P_2和ca的物种，其相称常数K_c计算为14-18。 C_4P_2的那些为4。此外，在速率常数为（2.4-2.5）X 10〜9 s〜（-1）的范围内，发生了从Ri〜（II）基供体到Os〜（II）基受体的快速分子内能量转移。 Dexter型机理和0.02 A〜（-1）的衰减因子（＃beta＃）形成的异双金属配合物。

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