Light-Enhanced Fluorescence of Multi-Level Cavitands Possessing Pyridazine Upper rim

Abstract

Completely different fluorescence behaviour of cavitands based on a same calix[4]resorcinarene compound was observed. While the fluorescence intensity of the parent compound, tetramethyl-cavitand (1) slowly faded as a result of UV-light exposure, the emission of the three-level cavitand with pyridazine moieties at the upper rim (5a) was enhanced by the excitation in the UV-region. The structure of fluorescence emission (characterized by excitation-emission matrices) and the absorption of 5a remained unaltered. The analysis of fluorescence decay curves reveals the presence of two separated components assigned to two individual emitting species. The measured significant increase of the average lifetime and quantum yield is the consequence of the UV-light induced transition between the different states of 5a. These observations can be explained by the structural difference between 5a and 1. As a counterpart of the naked cavitand (1) with methyl substituents at the upper rim only, 5a has three additional moieties benzene, triazole and pyridazine levels. Computational studies proved the existence of two conformational isomers of 5a. Upon ultraviolet light excitation a "dark" to "light" conformational transition occurs between the two isomers. This hypothesis was confirmed by anisotropy decay measurements.

Keywords: Conformational isomer; Fluorescence enhancement; Internal fluorescence quenching; Photochromism; Photoswitchable material; Triazole pyridazine cavitand.