Excited states of N,Si-chelated transition metal complexes: Characteristics of [sigma]-bond-to-ligand charge-transfer (SBLCT) excited states in fac-Ir[(6-isopropyl-8-quinolyl)diorganosilyl][sub 3]

Although the photoproperties of a variety of cyclometallated materials have been reported, relatively little is known with regard to the photoproperties of metallacyclic compounds in which group IV elements other than C are bonded to a transition metal center. However, the preparation of stable comp...

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Bibliographic Details
Published in:Inorganic chemistry 1993-10, Vol.32:22
Main Authors: Djurovich, P.I., Watts, R.J.
Format: Article
Language:English
Subjects:
400500 - Photochemistry
ABSORPTION SPECTROSCOPY
CHELATES
CHEMICAL REACTION YIELD
CHEMISTRY
COMPLEXES
ELECTRONIC STRUCTURE
EMISSION SPECTROSCOPY
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPLEXES
PHOTOCHEMISTRY
SILICON COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
YIELDS
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Summary:Although the photoproperties of a variety of cyclometallated materials have been reported, relatively little is known with regard to the photoproperties of metallacyclic compounds in which group IV elements other than C are bonded to a transition metal center. However, the preparation of stable complexes of P,Si-chelating ligands is well-documented, and several N,Si-chelated complexes of Re(I), Ir(III), and Rh(III) were recently reported. These types of complexes afford the opportunity to investigate the photochemical characteristics of materials containing metallacycles based upon M-Si rather than M-C bonds. The authors report here the initial characterizations of the excited states of several Si-Ir(III)-bonded complexes. These complexes are expected to have characteristics intermediate between those of C-M-bonded species and M[prime]-M-bonded materials where M[prime] is Ge, Sn, or Pb. Spectroscopic characteristics of the excited states of these Si-Ir(III)-bonded complexes bear a close resemblance to those reported for complexes containing Ge-Re(I) or Sn-Re(I) bonds. However, the photochemical characteristics of these complexes are distinct: associative quenching of the excited states in coordinating solvents is evident in the Si-Ir-(III)-bonded materials, while dissociative rupture of the Ge-Re(I) or Sn-Re(I) bond leads to high quantum yield photochemistry in the latter.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00074a006