Fourier-transform infrared spectroscopic studies of dithia tetraphenylporphine

We present here infrared absorption spectra of dithia tetraphenylporphine and its cation in the 450–1600 and 2900–3400 cm⁻¹ regions. Most of the allowed IR bands are observed in pairs due to overallD _2h point group symmetry of the molecule. The observed bands have been assigned to the porphyrin skeleton and phenyl ring modes. Some weak bands, which are forbidden underD _2h , also appear in the spectra due to the distortion of the molecule from planarity-caused by the out-of-plane positioned N and S atoms. Increased intensity of some phenyl ring bands compared to free-base tetraphenylporphine is explained on the basis of rotation of phenyl rings towards the mean molecular plane. Contrary to the point group symmetry of cation of dithia tetraphenylporphine, certain bands are observed to be degenerate due to identical bonding arrangements in pyrrole rings of the cation