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Photophysical Properties of Polypyridyl Carbonyl Complexes of Rhenium(I)

DOI: 10.1039/DT9910000849

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 849 - 858 (1991)

Update date:2022-08-06

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Authors:

Worl, Laura A.Worl, Laura A.

Duesing, RichDuesing, Rich

Chen, PingyunChen, Pingyun

Ciana, Leopoldo DellaCiana, Leopoldo Della

Meyer, Thomas J.Meyer, Thomas J.

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Article abstract of DOI:10.1039/DT9910000849

The photophysical properties of the metal to ligand charge transfer (m.l.c.t.) excited states of the complexes (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 x 1 s) (knr is the rate constant for nonradiative decay) and the Franck-Condon factor calculated from parameters obtained by emission spectral fitting.The solvent reorganizational energy for 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 polybipyridyl 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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Product name:fac-(4,4'-diphenyl-2,2'-bipyridine)chlororhenium(I)(CO)3

Cas No:134438-71-4

134438-71-4

R&D Labs maybe for 134438-71-4

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