Macrocyclic chemosensors with anthraquinone signaling unit built into ionophore. Experimental and computational studies (part I) - synthesis and effect of proton binding on spectrophotometric and electrochemical properties

Abstract

Two macrocyclic chemosensors with anthraquinone signaling unit incorporated into ionophore system (via positions 1 and 8) have been synthesized and subsequently their physicochemical properties became the subject of our extensive research. First ligand, labeled in the paper as AQ-Ncrown is characterized by a cyclic structure of a crown ether, while second one AQ-Ncrypt includes an additional ethoxy bridge, which ensures the bicyclic character of a cryptand. The studied macrocycles possess both oxygen and nitrogen heteroatoms in the ionophore cavity. Dualistic (chromophore and electrophore) signaling nature of described compounds, makes them potentially attractive molecular recognition systems. The aim of our research was to synthesize and analyze the spectroscopic, acid-base and redox properties of aforesaid macrocycles. Furthermore, we have combined experimental approach together with theoretical investigations. The equilibrium structures of AQ-Ncrown and AQ-Ncrypt were determined with the use of DFT calculations. The sensitivity of studied macrocycles towards interactions with protons was scrutinized. The complete pH-spectrophotometric characteristic of studied ligands together with their protolytic forms and corresponding pKa values were determined. The influence of medium (aprotic and protic solvent) on spectral effects was described. Furthermore, the molecular electrostatic potential maps for ligands and differential electron densities for their mono and dianions were calculated. The redox reactions was investigated at different pHs by cyclic voltammetry. Electrochemical results have presented intriguing phenomenon: the specific stabilization of the reduced form of the protonated molecules. The calculations have revealed that this is a consequence of barrierless intramolecular proton transfer (from the macrocycle cavity onto the anthraquinone moiety) that might occur during the reduction process in acidic medium.