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Photophysical Properties of a Series of Rhenium Selenide Cluster Complexes Containing Nitrogen‐Donor Ligands
Author(s) -
Wilson Wade B.,
Stark Kevin,
Johnson Dean B.,
Ren YiXin,
Ishida Hitoshi,
Cedeño David L.,
Szczepura Lisa F.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201301626
Subject(s) - chemistry , benzonitrile , excited state , rhenium , photochemistry , nitrile , ligand (biochemistry) , selenide , crystallography , inorganic chemistry , medicinal chemistry , organic chemistry , nuclear physics , biochemistry , physics , receptor , selenium
The photophysical properties of rhenium selenide cluster complexes containing various nitrogen‐donor ligands (nitrile, azide, tetrazolate, and triazolate) are reported. These octahedral clusters are all based on the site‐differentiated [Re 6 Se 8 ] 2+ core and have the general formula [Re 6 Se 8 (PEt 3 ) 5 L] n + (L = nitrogen‐donor ligand). The excited‐state lifetimes, emission quantum yields, the rates of radiative and nonradiative decay, and the rate of quenching with O 2 are reported for thirteen different cluster complexes. The longest excited‐state lifetime was found for [Re 6 Se 8 (PEt 3 ) 5 ( p ‐aminobenzonitrile)][BF 4 ] 2 . The series of benzonitrile and phenyl‐substituted tetrazolate complexes allowed us to investigate the electronic impact of the para substituent; electrochemical and computational studies support metal‐to‐ligand charge transfer character in the excited‐state wave function for the p ‐nitrobenzonitrile complex. Notably, the substituents of the benzonitrile ligands have a greater effect on the photophysical properties than the substituents of the phenyltetrazolate ring.