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

• Published in: ChemistrySelect (Weinheim) 2024-08, Vol.9 (30), p.n/a
• Main Authors: Priyambada Biswal, Supriya, Hota, Prabhudatta, Ranjan Dash, Manas, Kumari Misra, Pramila
• Format: Article
• Language: English
• Subjects: Hydroxy-substituted Anil; Hyperconjugative interaction energy; Mechanism of electron transport; Oscillator strength; Time-dependent density functional theory
• ISSN: 2365-6549; 2365-6549
• DOI: 10.1002/slct.202303788

The 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. DFT studies coupled with cyclic voltammetry confirmed that the two hydroxy‐substituted anils possess a suitable structural hierarchy to demonstrate electrochemical properties, which is essential for molecular‐based optoelectronic applications.