Options
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
Date Issued
2009
Date Available
2011-01-12T16:48:59Z
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.
[(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.
Sponsorship
Science Foundation Ireland
Irish Research Council for Science, Engineering and Technology
Other funder
Other Sponsorship
Netherlands Organisation for Scientific Research (NWO)
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
Subject – LCSH
Ruthenium
Osmium
Electrochemical analysis
Web versions
Language
English
Status of Item
Peer reviewed
This item is made available under a Creative Commons License
File(s)
Loading...
Name
Dalton Trans 2009 HV.pdf
Size
680.74 KB
Format
Adobe PDF
Checksum (MD5)
8b9911cc16da3271fc9f6a2d0e20643f
Owning collection