Photochemistry and photophysics of antimony(III) hyper porphyrins: activation of dioxygen induced by a reactive sp excited state

Observations of the photoredox reactivity of antimony(III) porphyrin complexes are reported. Upon irradiation with visible light under ambient conditions, a photooxidation to the corresponding dihydroxoantimony(V) porphyrins occurs. At the same time a two-electron or four-electron reduction of molec...

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Bibliographic Details
Published in:Inorganic chemistry 1994-01, Vol.33 (2), p.314-318
Main Authors: Knoer, Guenther, Vogler, Arnd
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
400500 - Photochemistry
ANTIMONY COMPLEXES
CARBOXYLIC ACIDS
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
Chemistry
COMPLEXES
ELECTRONIC STRUCTURE
ELEMENTS
Exact sciences and technology
General and physical chemistry
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MATHEMATICAL MODELS
NONMETALS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN
PHOTOCHEMICAL REACTIONS
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
PORPHYRINS
REDOX REACTIONS
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Summary:Observations of the photoredox reactivity of antimony(III) porphyrin complexes are reported. Upon irradiation with visible light under ambient conditions, a photooxidation to the corresponding dihydroxoantimony(V) porphyrins occurs. At the same time a two-electron or four-electron reduction of molecular oxygen takes place, depending on the experimental conditions. In the absence of suitable electron acceptors, a photoinduced disproportionation reaction occurs. The photolysis of antimony(III) porphyrins shows a pronounced wavelength dependence. The reactive excited state is concluded to be of the metal-centered sp type. An extended model for the electronic structure of p-type hyper metalloporphyrins is suggested.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00080a021