Ligand-assisted photochemical reaction of metalloporphyrins. Photodissociation of carbon-indium bond in ethylindium (III) tetraphenylporphyrin with the aid of axial pyridine
Ethylindium (III) tetraphenylporphyrin, C/sub 2/H/sub 5/In/sup III/TPP, undergoes photodissociation of the carbon-indium bond in the excited triplet state originating from the porphyrin ligand. The quantum yield, Phi, for the photodecomposition of C/sub 2/H/sub 5/In/sup III/TPP in benzene increases with an increase in pyridine concentration: Phi = 0.046 in the absence of pyridine and Phi = 0.3 at an infinite concentration of pyridine. From the quantum yield measurements and laser photolysis studies, it is concluded that the excited triplet states, /sup 3/C/sub 2/H/sub 5/In/sup III/TPP(Py)*, are in equilibrium:/sup 3/C/sub 2/H/sub 5/In/sup III/TPP* + Py ..cap alpha.. /sup 3/C/sub 2/H/sub 5/In/sup III/TPP(Py)*, where Py is a pyridine molecule. The equilibrium constant is determined as 6.45 X 10/sup 2/ M/sup -1/ at 20/sup 0/C. The increase in the quantum yield for the photodecomposition of C/sub 2/H/sub 5/In/sup III/TPP in the presence of pyridine is interpreted in terms of the facile dissociation of the carbon-indium bond in /sup 3/C/sub 2/H/sub 5/In/sup III/TPP(Py)* assisted by the axial pyridine.
- Research Organization:
- Institute of Physical and Chemical Research, Saitama, Japan
- OSTI ID:
- 5614432
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:17; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
AZINES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISSOCIATION
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INDIUM COMPLEXES
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PORPHYRINS
PYRIDINE
PYRIDINES
SPECTROSCOPY