Electron Transfer in Metal‐Organic Molecules. A Time Resolved EXAFS and Optical Spectroscopy Study
Electron Transfer in Metal‐Organic Molecules. A Time Resolved EXAFS and Optical Spectroscopy Study
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金属有机分子中的电子转移时间分辨 EXAFS 和光谱研究。
DOI：
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发表时间：
2011
期刊：
影响因子：
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通讯作者：
P. Rentzepis
中科院分区：
文献类型：
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作者：
Jie Chen;Wei;P. Rentzepis
我们通过超快 X 射线吸收和光谱测量了在 267 nm 飞秒脉冲激发后，M-O (M=Fe, Co) 和 Co-N 金属与配体键长随时间的变化以及激发态和中间物质的形成和衰减。这些实验数据与 DFT 计算相结合，使我们能够确定两种金属配体配合物 [M(III)(C2O4)3]3- 和 [Co(III)(NH3)6 ]3+ 氧化还原反应中电子转移的机理。根据数据我们发现，即使两个分子都被激发到其电荷转移带中，[M(III)(C2O4)3]3-的氧化还原反应通过分子间电子转移进行，而[Co(III)(NH3)6 ]3+电子转移机制是分子内电子转移。
We have measured, by means of ultrafast x-ray absorption and optical spectroscopy, the M-O (M=Fe, Co) and Co-N metal to ligand bond length change as a function of time and the formation and decay of the excited states and intermediate species, after excitation with a 267 nm femtosecond pulse. These experimental data combined with DFT calculations allowed us to determine the mechanism of electron transfer operating in the redox reaction of two metal-ligand complexes, [M(III)(C2O4)3]3- and [Co(III)(NH3)6 ]3+. Based on the data we find that, even though both molecules are excited into their charge transfer band, the redox reaction of [M(III)(C2O4)3]3- proceeds via intermolecular electron transfer while [Co(III)(NH3)6 ]3+ electron transfer mechanism is intramolecular.