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

Jie Chen | Zendy; Hua Zhang | Zendy; Ivan V. Tomov | Zendy; Xunliang Ding | Zendy; P. M. Rentzepis | Zendy

Open Access

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

Author(s) -

Jie Chen,

Hua Zhang,

Ivan V. Tomov,

Xunliang Ding,

P. M. Rentzepis

Publication year - 2008

Publication title -

proceedings of the national academy of sciences

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 5.011

H-Index - 771

eISSN - 1091-6490

pISSN - 0027-8424

DOI - 10.1073/pnas.0806990105

Subject(s) - photochemistry , ultrafast laser spectroscopy , electron transfer , chemistry , excited state , femtosecond , intramolecular force , dissociation (chemistry) , photodissociation , femtochemistry , excitation , spectroscopy , atomic physics , laser , stereochemistry , physics , electrical engineering , quantum mechanics , optics , engineering

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.

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