Photophysics of some substituted 3H-indole probe molecules and their charged species

Abstract

The spectroscopic and photophysical parameters of neutral and cationic species of the following molecules have been discussed: 2-phenyl-3,3-dimethyl-3H-indole (1), 2-[(p-amino)phenyl]-3,3-dimethyl-3H-indole (2), 2-[(p-dimethylamino)phenyl]-3,3-dimethyl-3H-indole (3), 2-[(p-amino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (4), 2-[(p-methylamino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (5), 2-[(p-dimethylamino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (6). Solvatochromic shifts have been interpreted in terms of the nature of the substituent groups and the state of solute–solvent interactions and complexation. The theoretical radiative decay rate constant [Formula: see text] along with the bandwidth of the absorption profile of the different species involved have been used to discuss the geometrical changes from one species to the other in the ground state. The mirror-image relationship between absorption and fluorescence spectra has proven to be a good tool to discuss any geometrical changes occurring in the excited state. A radiationless torsional mechanism takes place in the excited state relaxation of the various species. The protonation of the ring nitrogen atom generates a highly planar cationic species which retains its conformation in the relaxed excited state. The very effective quenching of the monocation fluorescence is interpreted by the formation of a non-emissive TICT state.