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Electron Transfer in Metal‐Organic Molecules. A Time Resolved EXAFS and Optical Spectroscopy Study
Author(s) -
Chen Jie,
Chen WeiKan,
Rentzepis Peter M.
Publication year - 2011
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201190001
Subject(s) - chemistry , intramolecular force , electron transfer , excited state , intermolecular force , ultrafast laser spectroscopy , spectroscopy , femtosecond , redox , photochemistry , molecule , absorption spectroscopy , atomic physics , inorganic chemistry , stereochemistry , laser , quantum mechanics , optics , physics , organic chemistry
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)(C 2 O 4 ) 3 ] 3‐ and [Co(III)(NH 3 ) 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)(C 2 O 4 ) 3 ] 3‐ proceeds via intermolecular electron transfer while [Co(III)(NH 3 ) 6 ] 3+ electron transfer mechanism is intramolecular.