Issue 21, 2009
From the journal:

Dalton Transactions

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†

Yvonne Halpin,a   Laura Cleary,a   Lynda Cassidy,a   Sabine Horne,‡a   Danilo Dini,a   Wesley R. Browneb  and  Johannes G. Vos*a  

* Corresponding authors

a Solar Energy Conversion SRC, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland
E-mail: han.vos@dcu.ie
Fax: +353-1-7005503
Tel: +353-1-7005307

b Centre for Systems Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, Groningen, The Netherlands

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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Article information

DOI
https://doi.org/10.1039/B823104D
Article type
Paper
Submitted
24 Dec 2008
Accepted
10 Mar 2009
First published
02 Apr 2009

Dalton Trans., 2009, 4146-4153

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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

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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