Spectroscopic investigation of the origin of distortion of guest coronene in various sites of n-heptane Shpol'skii matrix

Abstract

We report the high resolution emission (S1 → S0, T1 → S0) and laser single site singlet excitation (S1 ← S0) spectra for the various insertion sites of coronene in n-heptane cooled to 1.5 K. The observation of site splitting of doubly degenerate vibrations and weak electric dipole forbidden 0, 0 bands in the S1 → S0 and T1 → S0 spectra indicates that the ground state, the first excited singlet and lowest triplet states are all distorted. In these spectra, the intensity distribution of the various sites in the 0, 0 bands suggests that the distortion is different from site to site but similar in S0, S1 and T1. Identical ordering of the sites in S1 S0 and S1 S0 spectra as well as the observation of weak shifts in the vibrational frequencies in the two states implies the absence of strong pseudo Jahn-Teller forces in the first excited singlet state. We propose, further, that this is also true for the triplet state. This conclusion is supported by the similarity in zero-field splitting parameters of coronene and deuterated coronene. Taken together, these results indicate strongly that the distortion of coronene in n-heptane is primarily crystal field induced and is not greatly changed upon excitation of the molecule to its lowest excited states.