Time-resolved transient difference absorption spectra of iridium-silicon bonded complexes: evidence for a solvated intermediate formed via iridium-silicon bond cleavage

The transient time-resolved difference absorption spectra (100-4000 ns) of two fac-Ir[(6-isopropyl-8-quinolyl)-diorganosily][sub 3] complexes (diorgano = dimethyl or phenylmethyl) in nitrogen-saturated toluene have been measured. The spectra indicate that the initial excitation by a pulsed nitrogen...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1994, Vol.98 (2), p.396-397
Main Authors: Djurovich, Peter I, Watts, Richard J
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
400500 - Photochemistry
ABSORPTION SPECTRA
CHEMICAL BONDS
CHEMICAL REACTIONS
Chemistry
COMPLEXES
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ENERGY LEVELS
Exact sciences and technology
EXCITED STATES
General and physical chemistry
GROUND STATES
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPLEXES
LASER RADIATION
PHOTOCHEMICAL REACTIONS
Photochemistry
PHOTOLYSIS
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
RADIATIONS
RESOLUTION
SILICON COMPLEXES
SOLVATION
SPECTRA
TIME RESOLUTION
TIMING PROPERTIES
TRANSIENTS
TRANSITION ELEMENT COMPLEXES
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Description
Summary:The transient time-resolved difference absorption spectra (100-4000 ns) of two fac-Ir[(6-isopropyl-8-quinolyl)-diorganosily][sub 3] complexes (diorgano = dimethyl or phenylmethyl) in nitrogen-saturated toluene have been measured. The spectra indicate that the initial excitation by a pulsed nitrogen laser (10 ns, 337 nm) gives rise to a broad visible absorption characteristic of a quinoyl radical anion as well as bleaching of the ground-state absorption bands due to [sigma]-bond-to-ligand charge transfer. Regeneration of the bleaching occurs on the same time scale as the disappearance of transient absorption of the quinolyl radical anion following pulsed excitation of the dimethyl derivative; however, residual bleaching persists for several microseconds following the disappearance of the quinolyl radical anion subsequent to pulsed excitation of the phenylmethyl derivative. The results indicate transient formation of a solvated intermediate due to Ir-Si bond cleavage prior to eventual re-formation of the starting complex in the latter instance. 12 refs., 1 fig.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100053a007