Combined Experimental and Theoretical Investigation of the Electrochemical Behavior of Hydroxy‐Substituted Anils

Abstract

AbstractThe present work explored the electrochemical behavior of two organic compounds, o‐hydroxybenzylidene‐orthochloroaniline(Anil‐1) and o‐hydroxynaphthalidene‐orthochloro aniline(Anil‐2) through a series of theoretical and experimental investigations. The vibrational frequencies of two anilswere analyzed experimentally by FTIR and theoretically by DFT studies. A comparison of the frequencies with their unsubstituted analog, o‐hydroxybenzylideneaniline, confirmed the electron‐donating nature of the −Cl and −OH substituents in anils. The hyperconjugative interaction energy obtained from NBO analysis divulged the direction of the electron donation from the donor orbitals to the acceptor orbitals. UV‐visible studies illustrated prominent π→π* electronic transitions with significant oscillator strength(0.10–0.26) and molar extinction coefficient(~104) experimentally. Analysis of the global and local reactive descriptors of anils revealed a lower HOMO‐LUMO energy gap of Anil‐2(4.05 eV) than Anil‐1(4.46 eV), corroborating the order of decreasing reactivity to be Anil‐2>Anil‐1. The Cyclic Voltammetry studies disclosed the involvement of an oxidation process in Anil‐1 and Anil‐2 with a higher oxidation potential of Anil‐1 (1.43 V) than Anil‐2(1.31 V) due to the naphthyl moiety of the latter. However, the absence of a cathodic peak in both cases envisaged the irreversible nature of oxidation. The results demonstrated that both the anils could be suitable optical materials for microelectronics applications.