The effect of pressure on the photochemistry of tris(bipyridyl)chromium(III) ion |
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| Authors: | A. D. Kirk |
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| Affiliation: | Department of Chemistry, University of Victoria, P.O. Box 1700, Victoria, B.C. V8M 2Y2, Canada;Department of Chemistry, University of British Columbia, Vancouver, B.C. V6T 1Y6, Canada;Istituto Chimico dell''Università, Centro di Studio sulla Fotochimica e Reattività degli Stati Eccitati dei Composti di Coordinazione, Ferrara, Italy |
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| Abstract: | The quantum yield for the photoaquation of Cr(bpy)33+ in basic medium decreases with increasing pressure, with an apparent volume of activation of 3.8 ± 1.0 ml mol−1. From this value and that associated with the phosphorescence lifetime, the volumes of activation for non-radiative decay to the ground state and for formation of photoproduct are derived as −1.6 and +2.9 ml mol−1, respectively. The latter value is consistent with either an associative process with water entering from pockets between the ligands or a dissociative process involving one or both bonds to a bipyridyl ligand. |
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| Keywords: | Author to whom correspondence should be addressed. |
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