Effect of Metal Atom Perturbations on the Luminescent Spectra of Porphyrins

Abstract
The low‐temperature emission spectra of the dimethyl ester of mesoporphyrin IX and its divalent derivatives of cobalt, nickel, copper, zinc, palladium, cadmium, and barium have been obtained. Magnesium etioporphyrin(II) and zinc phthalocyanine were also investigated. The divalent silver mesoporphyrin was also studied, but no luminescence was obtained for this compound. Considerations of the relative lifetimes of fluorescence and phosphorescence of the various derivatives permit qualitative deductions to be made regarding magnetic susceptibility. Certain qualitative information on metal‐porphyrin bonding is presented based on the comparative intensities of fluorescence and phosphorescence. Anomolous emission characteristics of several of the metallo‐porphyrins are tentatively interpreted in terms of crossing of a first excited state and the ground state.

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