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Porphyrins. 40. Electronic spectra and four-orbital energies of free-base, zinc, copper, and palladium tetrakis(perfluorophenyl)porphyrins

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50204a021· OSTI ID:5313936
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Absorption and emission spectra and emission quantum yields are given for free-base (H/sub 2/), Zn, Cu, and Pd derivatives of tetrakis(perfluorophenyl)porphyrin (TFPP). The four-orbital model is used to rationalize differences in the optical properties among the derivatives of TFPP and the same derivatives of porphine (P), octaethylporphyrin (OEP), and tetraphenylporphyrin (TPP). It is concluded from absorption data that the energy difference between the two excited singlets, i.e., /sup 1/E(a/sub 2u/,e/sug g/) - /sup 1/E(a/sub 1u/,e/sub g/), decreases along the series Pd > Cu > Zn > H/sub 2/ and also along the series OEP > P > TFPP > TPP. The theory and date are reviewed, and it is concluded that the energy difference between the two excited triplets, i.e., /sup 3/E(a/sub 2u/,e/sub g/) - /sup 3/E(a/sub 1u/,e/sub g/), also decreases along these series. However the condition of degeneracy, e.g., /sup 1/E(a/sub 2u/,e/sub g/) - /sup 1/E(a/sub 1u/,e/sub g/) = 0, occurs for different molecules in the singlet and triplet cases. Theory also suggests that if /sup 3/E(a/sub 2u/,e/sub g/) > /sup 3/E(a/sub 1u/,e/sub g), the molecule should form a /sup 2/A/sub 1u/ cation radical and if /sup 3/E(a/sub 2u/,e/sub g/) < /sup 3/E(a/sub 1u/,e/sub g/) the molecule should form a /sup 2/A/sub 2u/ radical. 4 figures, 2 tables.

Research Organization:
Univ. of Washington, Seattle
OSTI ID:
5313936
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:2; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104* -- Spectral Procedures-- (-1987)
ABSORPTION SPECTRA
CARBOXYLIC ACIDS
COMPLEXES
COPPER COMPLEXES
ELECTRON SPECTRA
EMISSION SPECTRA
ENERGY LEVELS
EXCITED STATES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
OPTICAL PROPERTIES
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PALLADIUM COMPLEXES
PHYSICAL PROPERTIES
PORPHYRINS
SPECTRA
TRANSITION ELEMENT COMPLEXES
ZINC COMPLEXES