Sensitized photolysis and luminescence of the tris(ethylenediamine

Soc. , 1971, 93 (2), pp 339–345. DOI: 10.1021/ja00731a008. Publication Date: January 1971. ACS Legacy Archive. Cite this:J. Am. Chem. Soc. 93, 2, 33...
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Sensitized Photolysis and Luminescence of the Tris (ethylenediamine)chromium (111) Ion in Aqueous Solution V. Balzani,* R. Ballardini, M. T. Gandolfi, and L. Moggi

Contribution from the Istituto Chimico “G. Ciamician” dell‘ Universitd, Laboratorio di Fotochimica e Radiazioni # A k a Energia del C.N.R., Bologna, Italy, and the Istituto Chimico dell‘ Universitd, Centro di Studio sulla Fotochimica e Reattivith. degli Stati Eccitati dei Composti di Coordinazione del C.N.R., Ferrara, Ituly. Received M a y 12, 1970

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Abstract: The energy transfer from biacetyl to Cr(en)3a+has been investigated in aqueous solutions at 15’. The complex quenches the phosphorescent emission of biacetyl but leaves unchanged its fluorescence. Absorption of light by biacetyl leads to 2E, 4Az, phosphorescent emission by the complex (sensitized emission) and also causes the aquation reaction of the complex (sensitized reaction). The quenching of biacetyl phosphorescence by Crthe intensity of the sensitized emission, and the quantum yield of the sensitized reaction increase with increasing complex concentration and decrease with increasing oxygen concentration. The limit quantum yield of the sensitized reaction (-0.8) is noticeably higher than the quantum yield of the direct reaction (0.40). In contrast, the ratio between the limit quantum yield of the sensitized emission and the quantum yield of the direct emission is