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), Vol. 91:17
- Country of Publication:
- United States
- Language:
- English
Similar Records
Axial-ligand control of the photophysical behavior of ruthenium(II) tetraphenyl- and octaethylporphyrin. Contrasting properties of metalloporphyrin (. pi. ,. pi. *) and (d,. pi. *) excited states
Photoinduced decarbonylation from carbonyliron tetraphenylporphyrin in ethanol. Effects of axial imidazole studied by laser flash photolysis
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
INDIUM COMPLEXES
ELECTRONIC STRUCTURE
PHOTOCHEMICAL REACTIONS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
ABSORPTION SPECTROSCOPY
DISSOCIATION
EXCITED STATES
EXPERIMENTAL DATA
PHOTOCHEMISTRY
PYRIDINE
AZINES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ENERGY LEVELS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
SPECTROSCOPY
400500* - Photochemistry