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Tuning the Excited-State Deactivation Pathways of Dinuclear Ruthenium(II) 2,2’-Bipyridine Complexes Through Bridging Ligand Design

Abstract

A detailed photophysical investigation of two dinuclear ruthenium(II) complexes is reported. The two metallic centers were coordinated to a bis-2,2’-bipyridine bridging ligand, connected either through the para (Lp, Dp) or the meta position (Lm, Dm). The results obtained herein were compared to the prototypical [Ru(bpy)3]2+ parent compound. The formation of dinuclear complexes was accompanied by the expected increase in molar absorption coefficients, i.e. 12000 M–1cm–1, 17000 M–1cm–1, and 22000 M–1cm–1 at the lowest energy MLCTmax transition for [Ru(bpy)3]2+, Dm and Dp respectively. The Lp bridging ligand resulted in a ruthenium (II) dinuclear complex that absorbed more visible light, had a longer-lived and more delocalized excited-state compared to a complex with the Lm bridging ligand. Variable temperature measurements provided valuable information about activation energies to the uppermost 3MLCT state and the metal-centered (3MC) state, often accompanied by irreversible ligand-loss chemistry. At 298 K, 48% of [Ru(bpy)3]2+* excited-state underwent deactivation through the 3MC state, whereas this deactivation pathway remained practically unpopulated (<0.5%) in both dinuclear complexes.

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Article information


Submitted
01 Apr 2020
Accepted
21 May 2020
First published
22 May 2020

Dalton Trans., 2020, Accepted Manuscript
Article type
Paper

Tuning the Excited-State Deactivation Pathways of Dinuclear Ruthenium(II) 2,2’-Bipyridine Complexes Through Bridging Ligand Design

S. Cerfontaine, L. Troian-Gautier, S. Wehlin, F. Loiseau, E. Cauët and B. Elias, Dalton Trans., 2020, Accepted Manuscript , DOI: 10.1039/D0DT01216E

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