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), Journal Name: Inorg. Chem.; (United States) Vol. 22:9; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500* -- Photochemistry
ACETONITRILE
ALCOHOLS
ALUMINIUM COMPLEXES
BROMIDES
BROMINE COMPOUNDS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
DE-EXCITATION
DYES
ELECTROMAGNETIC RADIATION
EMISSION SPECTROSCOPY
ENERGY-LEVEL TRANSITIONS
ETHANOL
EXCITATION
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
LOW TEMPERATURE
MEDIUM TEMPERATURE
METHANOL
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
PHOTOCHEMISTRY
PHTHALOCYANINES
RADIATIONS
REDUCTION
REFRACTORY METAL COMPOUNDS
RHODIUM BROMIDES
RHODIUM CHLORIDES
RHODIUM COMPLEXES
RHODIUM COMPOUNDS
RUTHENIUM COMPLEXES
SOLVENTS
SPECTROSCOPY
TIME DEPENDENCE
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
ULTRAVIOLET RADIATION
WAVELENGTHS