SOLUTE-SOLVENT INTERACTION AND ITS EFFECT ON THE VIBRONIC AND VIBRATIONAL STRUCTURE OF PYRENE SPECTRA

Abstract— The enhancement of weakly allowed electronic and vibrational transitions of pyrene in polar solvents at room temperature has been studied by optical and infrared techniques. We previously reported the formation of molecular complexes between pyrene and alcohols by monitoring the changes in the fundamental stretching vibrational band of the —OH group of alcohols in the presence of pyrene. The infrared spectrum of pyrene in the region 1575–1700cm^-1 has been found in the present work to undergo changes in polar solvents, consistent with complex formation, with the appearance of new bands at wavenumbers where symmetry-forbidden transitions exist. The enhancement of weak bands in the electronic spectra is attributed to the reduction in the symmetry of the pyrene molecule brought about by complex formation. Further support for this interpretation is provided by the finding that I-methylpyrene, which has reduced symmetry, shows the enhancement in the electronic spectra and the appearance of new bands in the infrared spectra even in inert solvents. The anomalous behavior of aromatic solvents is discussed.