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

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 Bdark^ to Blight^ conformational transition occurs between the two isomers. This hypothesis was confirmed by anisotropy decay measurements

Exploiting non-covalent π interactions for catalyst design

Molecular recognition, binding and catalysis are often mediated by non-covalent interactions involving aromatic functional groups. Although the relative complexity of these so-called π interactions has made them challenging to study, theory and modelling have now reached the stage at which we can explain their physical origins and obtain reliable insight into their effects on molecular binding and chemical transformations. This offers opportunities for the rational manipulation of these complex non-covalent interactions and their direct incorporation into the design of small-molecule catalysts and enzymes