Photochemistry of transition-metal phthalocyanines. Mechanistic aspects of the photochemistry of the acido(phthalocyanine)rhodium(III) complexes investigated by continuous, flash, and laser flash photolysis
Rh(ph)(CH/sub 3/OH)X, X = Cl, Br, or I, has been prepared and characterized. Continuous-wave irradiations of these phthalocyanines in the ultraviolet region of the spectrum, in acetonitrile and acetonitrile-isopropyl alcohol mixtures, result in the redox-induced substitution of the axially coordinated halide ions by the solvent. Even though the overall reaction was photosubstitution, the intermediates observed by conventional and laser flash photolysis were found to be rhodium(II) phthalocyanine and rhodium(III) phthalocyanine ligand radicals. The photoredox processes were attributed to the population of (n..pi..*) ligand-centered excited states that involve the lone electron pair from the bridge nitrogens of the phthalocyanine ligand. 9 figures, 3 tables.
- OSTI ID:
- 6876537
- Journal Information:
- Inorg. Chem.; (United States), Vol. 21:8
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
PHOTOLYSIS
ABSORPTION SPECTRA
ACETONITRILE
ALCOHOLS
BROMIDES
CHEMICAL REACTION KINETICS
CHLORIDES
CYCLOALKENES
ELECTRON SPIN RESONANCE
EXCITATION
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDRATES
IODIDES
LASER RADIATION
LIGANDS
MIXTURES
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
PHOTOIONIZATION
PROPANOLS
WATER
ALKENES
BROMINE COMPOUNDS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COMPLEXES
DATA
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
ENERGY-LEVEL TRANSITIONS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IODINE COMPOUNDS
IONIZATION
KINETICS
MAGNETIC RESONANCE
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATIONS
REACTION KINETICS
RESONANCE
SOLVENTS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry
400201 - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)