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Published January 20, 1999 | public
Journal Article

Femtosecond Dynamics and Electrocatalysis of the Reduction of O_2: Tetraruthenated Cobalt Porphyrins

Abstract

Recently we reported the femtosecond dynamics of some porphyrin molecules. These studies elucidated the elementary steps involved in intramolecular relaxation and charge transfer (CT) in cobalt tetraphenylporphyrin (CoTPP) from the porphyrin π (a_(2u)) system to the Co(d_z^2). Our interest in the dynamics of intramolecular electron transfer stems from recent studies of cobalt porphyrins that were modified by attachment of Ru(II) or Os(II) complexes to the periphery of the porphyrin ring. These modified cobalt porphyrins exhibit high catalytic activity for the electroreduction of O_2 directly to H_2O, a process that most monomeric cobalt porphyrins are unable to accomplish. The mechanism by which the modified cobalt porphyrins achieve the direct, four-electron reduction of O_2 has been suggested to involve back-bonding interactions among the attached Ru(II) and Os(II) centers, the porphyrin ring, and the Co(II) ion at its center.

Additional Information

© 1999 American Chemical Society. Received October 6, 1998. Publication Date (Web): December 31, 1998. This work was supported by the National Science Foundation (Laboratory for Molecular Sciences). We wish to thank Mr. Björn Önfelt for his assistance with some of the experiments.

Additional details

Created:
August 19, 2023
Modified:
October 20, 2023