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Intramolecular energy-transfer processes in a bis(porphyrin)-ruthenium(II) bis(2,2′:6′,2″-terpyridine) molecular array

Lookup NU author(s): Professor Andrew Benniston, Emeritus Professor Anthony Harriman, Consuelo Pariani, Craig Sams

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Abstract

A molecular triad has been synthesized comprising two free-base porphyrin terminals linked to a central ruthenium(ii) bis(2,2′:6′,2″- terpyridine) subunit via meso-phenylene groups. Illumination into the ruthenium(ii) complex is accompanied by rapid intramolecular energy transfer from the metal-to-ligand, charge-transfer (MLCT) triplet to the lowest-energy π-π* triplet state localized on one of the porphyrin subunits. Transfer takes place from a vibrationally excited level which lowers the activation energy. The electronic coupling matrix element for this process is 73 cm-1. Selective illumination into the lowest-energy singlet excited state (S1) localized on the porphyrin leads to fast singlet-triplet energy transfer that populates the MLCT triplet state with high efficiency. This latter process occurs via Dexter-type electron exchange at room temperature, but the activation energy is high and the reaction is prohibited at low temperature. For this latter process, the electronic coupling matrix element is only 8 cm-1. © the Owner Societies 2006.


Publication metadata

Author(s): Benniston AC, Harriman A, Pariani C, Sams CA

Publication type: Article

Publication status: Published

Journal: Physical Chemistry Chemical Physics

Year: 2006

Volume: 8

Issue: 17

Pages: 2051-2057

Print publication date: 01/01/2006

ISSN (electronic): 1463-9076

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b600420b

DOI: 10.1039/b600420b


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