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DOI: 10.1039/A905783H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3729-3734

Excited state electronic properties of the [(phen)(OC)3ReI(NC)RuII(bpy)2(CN)]PF6 and [(phen)(OC)3ReI(CN)RuII(bpy)2(CN)]PF6 linkage isomers[hair space]†

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David W. Thompson, Jon R. Schoonover, Thomas J. Meyer, Roberto Argazzi and Carlo Alberto Bignozzi

Abstract

The results of temperature dependent emission lifetimes, emission spectral fitting and excited state transient absorption spectroscopy of the two hetero-dinuclear [(phen)(OC)3ReI(CN)RuII(bpy)2(CN)]+ and [(phen)(OC)3ReI(NC)RuII(bpy)2(CN)]+ linkage isomers (abbreviated Re–CN–Ru and Re–NC–Ru) have been examined. In both dinuclear species efficient intramolecular Re*→Ru energy transfer occurs, leading to population of emitting dπ(Ru)–π*(bpy), 3MLCT states. The temperature dependent emission data suggest that the barrier for the MLCT–dd surface crossing is smaller in magnitude when the “[(phen)(OC)3Re(NC)]” moiety is bound to the Ru(bpy)2(CN) emitting unit. This is interpreted as the result of its enhanced ability to backbond from RuII which increases the energy of the MLCT relative to the dd states.

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