Issue 37, 2015

Synergistic “ping-pong” energy transfer for efficient light activation in a chromophore–catalyst dyad

Abstract

The synthesis of a porphyrin–RuII polypyridine complex where the porphyrin acts as a photoactive unit and the RuII polypyridine as a catalytic precursor is described. Comparatively, the free base porphyrin was found to outperform the ruthenium based chromophore in the yield of light induced electron transfer. Mechanistic insights indicate the occurrence of a ping-pong energy transfer from the 1LC excited state of the porphyrin chromophore to the 3MCLT state of the catalyst and back to the 3LC excited state of the porphyrin unit. The latter, triplet–triplet energy transfer back to the chromophore, efficiently competes with fast radiationless deactivation of the excited state at the catalyst site. The energy thus recovered by the chromophore allows improved yield of formation of the oxidized form of the chromophore and concomitantly of the oxidation of the catalytic unit by intramolecular charge transfer. The presented results are among the rare examples where a porphyrin chromophore is successfully used to drive an oxidative activation process where reductive processes prevail in the literature.

Graphical abstract: Synergistic “ping-pong” energy transfer for efficient light activation in a chromophore–catalyst dyad

Supplementary files

Article information

Article type
Paper
Submitted
29 Jul 2015
Accepted
07 Aug 2015
First published
10 Aug 2015

Phys. Chem. Chem. Phys., 2015,17, 24166-24172

Author version available

Synergistic “ping-pong” energy transfer for efficient light activation in a chromophore–catalyst dyad

A. Quaranta, G. Charalambidis, C. Herrero, S. Margiola, W. Leibl, A. Coutsolelos and A. Aukauloo, Phys. Chem. Chem. Phys., 2015, 17, 24166 DOI: 10.1039/C5CP04458H

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