Calculation of Electron Transfer Rate Constants from Emission Spectra in Re(I) Chromophore−Quencher Complexes
Calculation of Electron Transfer Rate Constants from Emission Spectra in Re(I) Chromophore−Quencher Complexes
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DOI：
10.1021/ja960312v
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发表时间：
1996-10
影响因子：
15
通讯作者：
J. Claude;Darryl S. Williams;T. Meyer
中科院分区：
文献类型：
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作者：
J. Claude;Darryl S. Williams;T. Meyer
描述了在1,2-二氯乙烷中，fac-[(4,4 ' - r2bpy)ReI(CO)3(LA)]n+ （4,4 ' - r2bpy = 4,4 ' - r2 -2,2 ' -联吡啶，R = Me或tBu， LA =醌受体配体，苯[g]异喹啉-5,10-二酮（BIQD）， 2-氧-1,4-萘醌阴离子（ONQ-）， 1/2 2,6-二羟基蒽醌二离子（AFA2-），或吡啶受体，1 -甲基-6-氧喹啉（OQD））的光物理性质。在ReI→4,4′- r2bpy金属-配体电荷转移（MLCT）激发下，分子内电子转移导致了瞬态态fac-[(4,4′- r2bpy)ReII(CO)3(LA•-)]n+。它们通过发射光谱拟合和瞬态吸收测量来表征，对于LA = OQD，则通过瞬态红外测量来表征。激发态发射分析表明，电子给体和电子受体之间存在弱到中等程度的电子耦合，HDA从BIQD复合物的153 cm-1到OQD复合物的3.9 cm-1不等。瞬态是氧化还原分离的(R…
The photophysical properties of the chromophore−quencher complexes, fac-[(4,4‘-R2bpy)ReI(CO)3(LA)]n+ (4,4‘-R2bpy = 4,4‘-R2-2,2‘-bipyridine, R = Me or tBu, and LA = the quinone acceptor ligands, benz[g]isoquinoline-5,10-dione (BIQD), 2-oxy-1,4-naphthoquinone anion (ONQ-), 1/2 2,6-dihydroxyanthraquinone dianion (AFA2-), or the pyridinium acceptor, 1-methyl-6-oxyquinoline (OQD)) in 1,2-dichloroethane are described. Following ReI → 4,4‘-R2bpy metal-to-ligand charge transfer (MLCT) excitation, intramolecular electron transfer leads to the transients, fac-[(4,4‘-R2bpy)ReII(CO)3(LA•-)]n+. They have been characterized by emission spectral fitting and transient absorption measurements and, for LA = OQD, by transient infrared measurements. As shown by analysis of excited-state emission, there is weak-to-moderate electronic coupling between the electron donor and acceptor sites in the transients with HDA varying from 153 cm-1 for the BIQD complex to 3.9 cm-1 for the OQD complex. The transients are redox-separated (R...