PHOTOINDUCED ELECTRON TRANSFER OF 2,2'-BIPYRIDYL RUTHENIUM (II) ADSORBED ONTO POROUS VYCOR GLASS (PHOTOCHEMISTRY, ENERGY CONVERSION).
Item
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Title
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PHOTOINDUCED ELECTRON TRANSFER OF 2,2'-BIPYRIDYL RUTHENIUM (II) ADSORBED ONTO POROUS VYCOR GLASS (PHOTOCHEMISTRY, ENERGY CONVERSION).
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Identifier
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AAI8629737
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identifier
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8629737
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Creator
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SHI, WEI.
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Contributor
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Harry D. Gafney
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Date
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1986
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Inorganic
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Abstract
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The spectroscopic and photophysical properties of 2,2'-bipyridyl ruthenium(II), Ru(bpy)(,3)('2+), adsorbed onto Corning's code 7930 porous Vycor glass, PVG, were studied. The UV-visible, resonance Raman, and luminescence spectra of the adsorbed complex resemble those of the aqueous solution, establishing that the complex retains its coordination sphere upon adsorption. However, considerable discrepancies were observed in the emission quantum yield, the excited state lifetime, and relative intensities of resonance Raman bands between the adsorbed complex and that in fluid solution. These differences are explained on the basis of the constraints imposed by the rigid environment of PVG on the adsorbed complex. Emission polarization measurements show that, indeed, the adsorbed Ru(bpy)(,3)('2+) is tightly held by the surface groups and its rotational and translational motions are severly curtailed.;The emission of adsorbed Ru(bpy)(,3)('2+) is quenched by coadsorbed cations Fe('3+), Cu('2+), and MV('2+) via electron transfer, and Cr('3+) via energy transfer mechanisms. Because of the slow diffusion on surface, quenching kinetics are found to be sensitive to the distributions of the reagents which, due to their different chemical and geometrical properties, adsorb onto different regions of the PVG surface. Consequently, non-linear Stern-Volmer behavior is found in most cases. The slow diffusion of reagents on surface is also responsible for the lack of significant lifetime quenching of the Ru(bpy)(,3)('2+) emission on PVG.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
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Program
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Chemistry
