Electronic structures of halogenated porphyrins. Spectroscopic properties of ZnTFPPX[sub 8] (TFPPX[sub 8] = octa-[beta]-halotetrakis(pentafluorophenyl)porphyrin; X = Cl, Br)
Journal Article
·
· Journal of the American Chemical Society; (United States)
- California Inst. of Technology, Pasadena, CA (United States)
We report here spectroscopic and theoretical (AM1) studies on zinc(II) octa-[beta]-halotetrakis(pentafluorophenyl)-porphyrins (ZnTFPPX[sub 8]; X = Cl, Br) that show a red shift in the Soret and Q absorption bands attributable to substituent-induced saddling of the macrocycle. The electronic effect of the halogens is to reduce the energies of both the HOMOs and LUMOs; however, this stabilization of orbital energies is counteracted by the distortion of the macrocycle, which results in a large destabilization of the porphyrin HOMOs and a smaller destabilization of the LUMOs. The net result is a slight increase in stability of the HOMOs and a greater stabilization of the LUMOs. Lowering the energies of the porphyrin HOMOs is an important factor to consider in the development of robust porphyrin catalysts. 25 refs., 1 fig., 3 tabs.
- OSTI ID:
- 6730511
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:21; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ABSORPTION SPECTRA
BROMINE COMPOUNDS
CALCULATION METHODS
CARBOXYLIC ACIDS
CATALYSTS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COMPLEXES
ELECTRONIC STRUCTURE
FLUORINE COMPOUNDS
HALOGEN COMPOUNDS
HALOGENATION
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
MOLECULAR ORBITAL METHOD
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
SPECTRA
STABILITY
STABILIZATION
ZINC COMPLEXES
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ABSORPTION SPECTRA
BROMINE COMPOUNDS
CALCULATION METHODS
CARBOXYLIC ACIDS
CATALYSTS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COMPLEXES
ELECTRONIC STRUCTURE
FLUORINE COMPOUNDS
HALOGEN COMPOUNDS
HALOGENATION
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
MOLECULAR ORBITAL METHOD
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
SPECTRA
STABILITY
STABILIZATION
ZINC COMPLEXES