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Excited state localization and internuclear interactions in asymmetric Ruthenium (II) and Osmium (II) bpy/tpy based dinuclear compounds
Date Issued
2010-02
Date Available
2010-11-24T15:19:06Z
Abstract
The synthesis of two asymmetric dinuclear complexes with the formula [M(bpy)2(bpt)Ru(tpy)Cl]2+, where M = Ru (1a), Os(2a); bpy = 2,2’-bipyridyl; Hbpt = 3,5-bis(pyridin-2-yl)1,2,4-triazole and tpy = 2,2’,6’,2”-terpyridine, is reported. The compounds obtained are characterized by mass spectrometry, 1H-NMR, UV/vis/NIR absorption, luminescence and resonance Raman spectroscopy. Deuterium isotope labeling facilitates assignment of the 1H-NMR and resonance Raman spectra. The interaction between the two metal centers, mediated by the bridging 1,2,4-triazolato moiety in the mixed valent state, is assigned as type II based on the observation of metal to metal charge transfer absorption bands at 7090 and 5990 cm-1 for 1a and 2a, respectively. The extent of localization of the emissive excited state was determined by transient resonance Raman and emission spectroscopy. Both 1a and 2a show phosphorescence at the same wavelengths; however, whereas for compound 1a the emission is based on the Ru(tpy)Cl- center, for 2a the emissive state is localized on the Os(bpy)2- unit. This indicates that also in the excited state there is efficient interaction between the two metal centers.
Sponsorship
Irish Research Council for Science, Engineering and Technology
Other Sponsorship
Libyan Government
Netherlands Science Foundation
Type of Material
Journal Article
Publisher
ACS Publications
Journal
Inorganic Chemistry
Volume
49
Issue
6
Start Page
2799
End Page
2807
Copyright (Published Version)
2010 American Chemical Society
Subject – LCSH
Ruthenium
Osmium
Raman spectroscopy
Web versions
Language
English
Status of Item
Peer reviewed
ISSN
0020-1669
This item is made available under a Creative Commons License
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