ISSN:
1434-1948
Keywords:
Zinc
;
Metalloporphyrins
;
Porphyrins
;
Cations
;
Radicals
;
ESR
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Zinc(II) complexes of substituted tetraphenylporphyrins, Zn[T(X-P)P], where X = H, p-F, p-Cl, m-Cl, p-CH3O, and m-CH3O, have been synthesized and characterized. Peripheral substitution shows marked changes in the chemical shifts of the phenyl proton resonances and E1/2 values of the redox couples in the anodic region while the UV/Vis spectra are unaffected. The monocation radicals of these complexes are generated by chemical oxidation with bromine. The ESR spectra reveal the formation of two types of radical species, Zn[T(X-P)P]+·Br- (species I) and Zn[T(X-P)(Brn-P)]+·Br- (species II): Species I at 298 K shows a spectrum, with well-resolved bromine hyperfine features, characteristic of a 2A2u electronic ground state while species II, except for the complex with X = m-CH3O, shows a featureless, isotropic resonance attributable to a 2A1u state. Zn[T(m-CH3O-P)(Brn-P)]+·Br-, on the other hand, exhibits nine resolved nitrogen hyperfine features corresponding to a 2A2u state. Variable temperature ESR spectra (77-298 K) indicate reduction in the bromine and nitrogen hyperfine coupling constants and an increase in the g value of species I from 2.0049 to 2.0060 with lowering temperature and suggest a labile electronic ground state for species I. The p-CH3O substituted complex exhibits an electronic transformation from 2A2u to 2A1u while the remaining complexes, including m-CH3O, show a transformation from 2A2u to an admixed 2A1u/2A2u state. The effect of substitution on the variable temperature ESR spectra are discussed.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
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