Raman Spectra of Porphyrins

Abstract

The spectroscopy of porphyrins has been developing rapidly during the last two decades, this class of compounds being of great biological importance and possessing a number of significant properties. Different spectroscopic techniques, viz., electronic spectroscopy including fine-structure quasiline spectra (Shpolsky effect), infrared spectroscopy, luminescence, flash photolysis, ESR and NMR spectroscopy etc., have been applied to the study of these molecules (see reference ¹ for a review). However until recently there were no publications on Raman spectra of porphyrins and related compounds although it is evident that a complete analysis of molecular vibrations is impossible without knowing the Raman frequencies, especially for centrosymmetrical molecules. We have obtained Raman spectra of two porphin derivatives, viz., copper and nickel octamethylporphin ² which seems to be, together with data on hemoglobin and cytochrome^3-5 and on chlorophylls ⁶, the first observation of Raman spectra of porphyrins. In this paper Raman spectra of several metalloporphyrins are presented including metal complexes of porphin, octamethylporphin, etioporphyrin I, meso-tetraphenylporphin and tetrabenzporphin. For some of them Shpolsky spectra have been obtained and a juxtaposition is made of the two kinds of spectral data concerning the frequencies of molecular no- modss. Also some data of infrared spectra are presented.