Linkage between Fluorescence and Electrochemical Properties of Imidazolium Compounds in Acetonitrile Solution

The fluorescence properties of some imidazolium derivatives are relevant in photosensing and therefore, the structural analysis of them is a key point for its rational design, which would be useful to prepare new systems with novel applications. Herein we report a multidisciplinary study of the fluorescence and voltammetric properties of three imidazolium compounds {1,3-bis[(R,R)-1 '-chloro-1 '-phenylpropan-2 '-yl]-imidazolium chloride (1), 1,3-bis[(Z)-1 '-phenylprop-1 '-en-2 '-yl]imidazolium chloride (2) 1,3-bis[(R)-1 '-chlorobutan-2 '-yl]-imidazolium chloride (3)}. Electronic structure calculations and Bader analyses were used to correlate both fluorescence and the capability of the molecules to be reduced through a heterogeneous electron transfer process. Both properties are strongly dependent on the proton in position two of the imidazolium ring, where the electron transfer as well as the excitation of the electrons are carried out. The reactivity in this position is controlled by the N-substituents on the imidazolium ring and is due to single contacts H...Cl-, tricentric contacts Cl...Cl-...Cl, pi-electronic delocalization and pi-stacking interactions.