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Issue 21, 2009
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Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

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Abstract

A series of binuclear ruthenium and osmium complexes [(bipy)2Ru(qpy)Ru(bipy)2]4+ (1), [(bipy)2Os(qpy)Os(bipy)2]4+ (2), [(bipy)2Ru(pytr-bipy)Ru(bipy)2]3+ (3), [(bipy)2Ru(pytr-bipy)Os(bipy)2]3+ (4), [(bipy)2Os(pytr-bipy)Ru(bipy)2]3+(5) and [(bipy)2Os(bpbt)Os(bipy)2]2+ (6) {bipy = 2,2′-bipyridyl; qpy = 2,2′:5′,5″:2″,2‴-quaterpyridyl; pytr-bipy = 3-(2,2′-bipyrid-6-yl)-5-(pyrid-2-yl)-1,2,4-triazolato, and bpbt = 5,5′-bis-(pyrid-2″-yl)-3,3′-bis-1,2,4-triazolato} are reported. Analysis of the electrochemical data focuses on structural factors and on determining the extent of electronic communication between the metal centres in the mixed valence oxidation state. Intervalence charge transfer (IT) bands could be identified in the spectra of the complexes 4 and 6 only. Analysis of their spectroelectrochemical data leads to the conclusion that the IT is superexchange mediated through the HOMO of the bridging ligand.

Graphical abstract: Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

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Supplementary files

Article information


Submitted
24 Dec 2008
Accepted
10 Mar 2009
First published
02 Apr 2009

Dalton Trans., 2009, 4146-4153
Article type
Paper

Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

Y. Halpin, L. Cleary, L. Cassidy, S. Horne, D. Dini, W. R. Browne and J. G. Vos, Dalton Trans., 2009, 4146
DOI: 10.1039/B823104D

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