Zeolite-mediated photochemical charge separation using a surface-entrapped ruthenium-polypyridyl complex

Abstract

Employing the strategy of quaternization of the 2,2' N atoms of the conjugated bipyridine ligand 1,4-bis[2-(4'-methyl-2,2'-bipyrid-4-yl)ethenyl]benzene (L), a polypyridyl complex of ruthenium(II) was tethered on the surface of zeolite Y. Electrochemical and spectroscopic properties of the complex suggest that, upon visible photoexcitation of the MLCT band, the electron is localized on the conjugated ligand rather than the bipyridines. Electron transfer from the surface complex to bipyridinium ions (methyl viologen) within the zeolite was observed. Visible light photolysis of the ruthenium-zeolite solid ion-exchanged with diquat and suspended in a propyl viologen sulfonate solution led to permanent formation of the blue propyl viologen sulfonate radical ion in solution. The model that is proposed involves intrazeolitic charge transfer to ion-exchanged diquat followed by interfacial (zeolite to solution) electron transfer to propyl viologen sulfonate in solution. Because of the slow intramolecular back-electron-transfer reaction and the forward electron propagation via the ion-exchanged diquat, Ru(III) is formed. This Ru(III) complex formed on the zeolite is proposed to react rapidly with water in the presence of light, followed by reaction with the propyl viologen sulfonate, to form pyridones and regeneration of Ru(II), which then continues the photochemical process.