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Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.


ABSTRACT: The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

SUBMITTER: Chen J 

PROVIDER: S-EPMC2563110 | biostudies-literature | 2008 Oct

REPOSITORIES: biostudies-literature

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Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.

Chen Jie J   Zhang Hua H   Tomov Ivan V IV   Ding Xunliang X   Rentzepis Peter M PM  

Proceedings of the National Academy of Sciences of the United States of America 20081001 40


The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reac  ...[more]

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