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Laser photolysis studies on the electron-transfer reaction from the photoexcited triplet state of chloroindium(III) tetraphenylporphyrin to methylviologen in methanol solutions

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100249a021· OSTI ID:5312014
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Laser photolysis studies were carried out for chloroindium (III) tetraphenylporphyrin, C1In/sup III/TPP, in methanol solutions. The triplet states of (In/sup III/)/sup +/TPP and methylviologen, MV/sup 2 +/, were found to form a triplet exciplex with an association constant of 6.5 x 10/sup 2/M/sup -1/. The triplet exciplex partly dissociates to the cation radical of (In/sup III/)/sup +/TPP, (In/sup III/)/sup +/TPP/sup +/), and methylviologen cation radical, MV/sup +/, followed by the back electron transfer from MV/sup +/ to ((In/sup III/)/sup +/TPP/sup +/) to regenerate MV/sup 2 +/ and (In/sup III/)/sup +/TPP. The triplet exciplex reacts with triethanolamine, TEA, presumably to produce a new triplet exciplex, /sup 3/((In/sup III/)/sup +/TPP(TEA)(MV/sup 2 +/)), in which a TEA molecule is considered to occupy the axial position. No ionic dissociation from this triplet exciplex was observed. Photolysis of the methanol solution of C1In/sup III/TPP containing 0.5 M TEA and 10-/sup 3/ M MV/sup 2 +/ gives rise to the formation of MV/sup +/ as a final product. The absorption spectroscopy study revealed that C1In/sup III/TPP in a methanol solution at 0.5 M TEA is transformed to (In/sup III/TPP(TEA)/sub 2/)/sup +/(C1/sup -/), in which two TEA molecules are located in the axial positions. On the basis of the laser photolysis study the triplet state of (In/sup III/TPP(TEA)/sub 2/)/sup +/ is confirmed to undergo efficient electron transfer toward MV/sup 2 +/, resulting in the formation of MV/sup 2 +/. 29 refs., 6 figs.

Research Organization:
Institute of Physical and Chemical Research, Wako, Japan; Gunma Univ., Kiryu, Japan
OSTI ID:
5312014
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:3; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
AZINES
BIPYRIDINES
CARBOXYLIC ACIDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DATA
DECOMPOSITION
ELECTRON TRANSFER
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INDIUM CHLORIDES
INDIUM COMPLEXES
INDIUM COMPOUNDS
INFORMATION
KINETICS
LASERS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PORPHYRINS
PYRIDINES
REACTION KINETICS
SPECTROSCOPY