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Influence of the ligand structure on the electrochemical and spectroscopic properties of ruthenium(II)-polypyridine complexes

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00271a029· OSTI ID:5370700
Extended Hueckel molecular orbital (EHMO) calculations on 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), and other unsubstituted polypyridine-type molecules have been performed to study the effect of the ligand structure on the spectroscopic and electrochemical properties of Ru(II)-polypyridine complexes. The obtained LUMO energies have been found to correlate with the first reduction potential of LL' and with the first reduction potentials of Ru(LL')/sub 3//sup 2 +/ or Ru(LL)/sub 2/(LL')/sup 2 +/ complexes, where LL' is a ligand easier to reduce than LL. Correlations between optical and electrochemical data of the same complexes have also been examined. Complexes containing LL' = taphen, DP or i-biq (taphen = dipyrido(3,2-c:2',3'-e)pyridazine, DP = dipyrido-(3,2-a:2',3'-c)phenazine, i-biq = 3,3'biisoquinoline) show an anomalous electrochemical and/or spectroscopic behavior. Possible reasons for such anomalies are discussed.
Research Organization:
Istituto FRAE-CNR, Bologna, Italy
OSTI ID:
5370700
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:24; ISSN INOCA
Country of Publication:
United States
Language:
English