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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Title: 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
Authors: Halpin, Yvonne
Cleary, Laura
Cassidy, Lynda
Horn, Sabine
Dini, Danilo
Browne, Wesley R.
Vos, Johannes G.
Permanent link: http://hdl.handle.net/10197/2704
Date: 2009
Abstract: A series of binuclear ruthenium and osmium complexes [(bipy)2Ru(qpy)Ru(bipy)2]4+ (1), [(bipy)2-Os(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 = 2,2¹-bipyridyl; qpy = 2,2¹:5¹,5¹¹:2¹¹,2¹¹¹-quaterpyridyl; pytr-bipy = 3-(2,2¹-bipyrid-6-yl)-5-(pyrid-2-yl)-1,2,4-triazolato, and bpbt = 5,5¹-bis-(pyrid-2¹¹-yl)-3,3¹-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.
Funding Details: Science Foundation Ireland
Irish Research Council for Science, Engineering and Technology
Other funder
Type of material: Journal Article
Publisher: RSC publications
Journal: Dalton Transactions
Volume: 21
Start page: 4146
End page: 4153
Copyright (published version): The Royal Society of Chemistry 2009
Keywords: RutheniumHOMOOsmiumSpectroelectrochemical
Subject LCSH: Ruthenium
Osmium
Electrochemical analysis
DOI: 10.1039/b823104d
Other versions: http://dx.doi.org/10.1039/B823104D
Language: en
Status of Item: Peer reviewed
Appears in Collections:Solar Energy Conversion (SEC) Cluster Research Collection

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