Charge transfer complexes of quinones in aqueous medium: Spectroscopic and theoretical studies on interaction of cimetidine with novel substituted 1,4-benzoquinones and its application in colorimetric sensing of anions

Abstract

For the first time, the charge transfer (CT) complexes of quinones in aqueous medium have been reported. A series of novel water soluble 1,4-benzoquinones possessing variable number of chloro and methoxy substituents has been employed as electron acceptors (MQ1−4) in the CT complexation with cimetidine (CTD) drug. The mechanism of the interaction has been investigated using various spectral techniques such as UV–Vis, 1H NMR and FT-IR spectra. The rate of the CT interaction was observed to decrease with progressive replacement of chloro by methoxy substituent in the quinone and this variation is well supported by the formation constant and enthalpy of activation values. Ab initio DFT calculations predicted that the variation in the bond lengths of the carbonyl moieties and the charge densities on the carbonyl oxygen atoms depend largely on the nature of the substituent present in the quinone ring. Also, the HOMODonor–LUMOAcceptor energy gaps correlate linearly with the formation constants of the CT complex. The equilibrium, kinetic, electrochemical and theoretical investigations of the CT interaction of these quinones indicated that progressive replacement of electron withdrawing chlorine atom (−I effect) by an electron releasing methoxy group (+M effect) makes these acceptors progressively weaker. The charge-transfer complex, formed between CTD and monomethoxy quinone derivative, has been employed as a new class of chromogenic sensor for the colorimetric sensing of fluoride and acetate ions.