Photophysical and photoelectrochemical properties of the bis(2,2′-bipyridine)(4,4′-dimethylthio-2,2′-bipyridine)ruthenium(II) complex

The chemistry and photophysics of a new ruthenium(II)–polypyridine complex, [Ru(bipy) 2(Sbipy)] 2+ where bipy=2,2′-bipyridine and Sbipy=4,4′-dimethylthio-2,2′-bipyridine, have been investigated. In spite of the thioether substituents in the 4,4′ positions of the 2,2′-bipyridine ligand, this complex...

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Bibliographic Details
Published in:	Journal of photochemistry and photobiology. A, Chemistry. Vol. 135; no. 2; pp. 185 - 191
Main Authors:	Toma, Henrique E, Serrasqueiro, Ricardo M, Rocha, Reginaldo C, Demets, Gregoire J.F, Winnischofer, Herbert, Araki, Koiti, Ribeiro, Paulo E.A, Donnici, Claudio L
Format:	Journal Article
Language:	English
Published:	Lausanne Elsevier B.V 2000 Elsevier Science
Subjects:	Chemistry Electrochemistry Exact sciences and technology General and physical chemistry Pentacyanoferrate Photoelectrochemistry Photoelectrochemistry. Electrochemiluminescence Polynuclear complexes Ruthenium polypyridines Polynuclear complexes Photoelectrochemistry Electrochemistry Pentacyanoferrate Ruthenium polypyridines Cationic complex MO method Molecular structure Organic ligand Theoretical study Transition metal Complexes Experimental study Cyclic voltammetry Organic solvent Near ultraviolet radiation Solution structure Complexes Mixed Visible radiation Ruthenium Complexes Platinoid Complexes Electronic transition Semiempirical method Chronoamperometry INDO S method Ultraviolet visible spectrometry
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Summary:	The chemistry and photophysics of a new ruthenium(II)–polypyridine complex, [Ru(bipy) 2(Sbipy)] 2+ where bipy=2,2′-bipyridine and Sbipy=4,4′-dimethylthio-2,2′-bipyridine, have been investigated. In spite of the thioether substituents in the 4,4′ positions of the 2,2′-bipyridine ligand, this complex behaves similarly to the [Ru(bipy) 3] 2+ complex, exhibiting strong charge-transfer bands at 450 nm, and luminescence emission at 630 nm ( t 1/2=0.91 μs), at room temperature. The time resolved excited state spectrum was simulated using the open-shell ZINDO/S method, indicating a rather complex composition of metal-to-ligand, ligand-to-metal and ligand-to-ligand charge-transfer transitions. The thioether groups have been exploited as strong binding sites for pentacyanoferrate ions, allowing the generation of polynuclear species suitable for immobilization purposes, onto nickel electrode surfaces. Such Prussian blue type films displayed photoaction response to visible light in the presence of dissolved oxygen.
ISSN:	1010-6030 1873-2666
DOI:	10.1016/S1010-6030(00)00293-8