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

Journal Article · Sun Aug 01 00:00:00 EDT 1982 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00138a010· OSTI ID:6876537

Muralidharan, S; Ferraudi, G; Schmatz, K

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), Journal Name: Inorg. Chem.; (United States) Vol. 21:8; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ABSORPTION SPECTRA
ACETONITRILE
ALCOHOLS
ALKENES
BROMIDES
BROMINE COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
CYCLOALKENES
DATA
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDRATES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IODIDES
IODINE COMPOUNDS
IONIZATION
KINETICS
LASER RADIATION
LIGANDS
MAGNETIC RESONANCE
MIXTURES
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOIONIZATION
PHOTOLYSIS
PROPANOLS
RADIATIONS
REACTION KINETICS
RESONANCE
RHODIUM COMPLEXES
SOLVENTS
SPECTRA
TRANSITION ELEMENT COMPLEXES
WATER