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Issue S, 1991
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Photophysical properties of polypyridyl carbonyl complexes of rhenium(I)


The photophysical properties of the metal to ligand charge transfer (m.l.c.t.) excited states of the complexes [Re(4,4′-X2-bipy)(CO)3Cl](X = NH2, NEt2, NHCOCH3, OCH3, CH3, H, Ph, Cl, CO2Et or NO2; bipy = bipyridine) vary systematically as the substituent X is varied. For the cases where m.l.c.t. states are lowest lying a quantitative correlation exists between ln (knr× 1 s)(knr is the rate constant for non-radiative decay) and the Franck–Condon factor calculated from parameters obtained by emission spectral fitting. The solvent reorganizational energy for [Re(bipy)(CO)3Cl] has been determined to be 1100 cm–1 in EtOH–MeOH (4:1 v/v) and 650 cm–1 in 2-methyltetrahydrofuran by a temperature dependent bandwidth study. Based on a comparative analysis of properties with related polypyridyl complexes of RuII and OsII it has been concluded that: (1) the extent of distortion at the 4,4′-X2-bipy acceptor ligand correlates with the energy gap between the excited and ground states; these results are in agreement with an earlier correlation found for polypyridyl complexes of OsII; (2) the unusually large Stokes shift and the broadening of the vibronic components in absorption and emission spectra arise from a combination of increased solvent reorganizational energies and greater distortions in the low-frequency modes between the excited and ground states; and (3) the relatively short lifetimes for the complexes of ReI have as a major contributing factor the participation of a ν(CO) mode at ca. 2020–2040 cm–1 as an energy acceptor in non-radiative decay.

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Article type: Paper
DOI: 10.1039/DT9910000849
Citation: J. Chem. Soc., Dalton Trans., 1991,0, 849-858

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    Photophysical properties of polypyridyl carbonyl complexes of rhenium(I)

    L. A. Worl, R. Duesing, P. Chen, L. D. Ciana and T. J. Meyer, J. Chem. Soc., Dalton Trans., 1991, 0, 849
    DOI: 10.1039/DT9910000849

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