Photochemistry of transition-metal phthalocyanines. Analysis of the photochemical and photophysical properties of the acido(phthalocyaninato)rhodium(III) complexes
The ultraviolet photochemistry of the rhodium(III) phthalocyanines Rh(ph)(CH/sub 3/OH)X with X = Cl/sup -/, Br/sup -/, and I/sup -/ was investigated at different wavelengths. The same action spectrum for the photoinduced hydrogen abstraction was obtained for the three compounds. The photonic energy of the excitation is degraded in part by emission at short wavelengths, e.g. lambda/sub max/ approx. = 420 nm. Such a violet emission, observed with phthalocyanines of Al(III), Rh(III), Co(III), and Ru(II), has been attributed to the relaxation of an upper /sup 3/pipi* excited state. The emission spectra at 77 K exhibited vibronic components with a separation between successive peaks ..delta..v approx. = 1.3 x 10/sup 3/ cm/sup -1/. A comparison between the excitation and action spectra shows the difference in the paths that populate the reactive npi* and upper emissive pipi* states. An investigation of the time dependence of the upper /sup 3/pipi* emission and lowest /sup 3/pipi* absorptions reveals the participation of triplet sublevels in the degradation of the excitation energy. The relationship between photoemissive and photoreactive states is discussed. 40 references, 6 figures, 2 tables.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 6102649
- Journal Information:
- Inorg. Chem.; (United States), Vol. 22:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
DE-EXCITATION
EXCITATION
PHOTOCHEMISTRY
REDUCTION
ACETONITRILE
ALUMINIUM COMPLEXES
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
EMISSION SPECTROSCOPY
ETHANOL
EXPERIMENTAL DATA
LOW TEMPERATURE
MEDIUM TEMPERATURE
METHANOL
ORGANIC SOLVENTS
PHTHALOCYANINES
RHODIUM BROMIDES
RHODIUM CHLORIDES
RHODIUM COMPOUNDS
RUTHENIUM COMPLEXES
TIME DEPENDENCE
ULTRAVIOLET RADIATION
WAVELENGTHS
ALCOHOLS
BROMIDES
BROMINE COMPOUNDS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DATA
DYES
ELECTROMAGNETIC RADIATION
ENERGY-LEVEL TRANSITIONS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADIATIONS
REFRACTORY METAL COMPOUNDS
SOLVENTS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400500* - Photochemistry