Role of π-electron conjugation in determining the electrical responsive properties of polychlorinated biphenyls: a DFT based computational study

Abstract

Global reactivity descriptors e.g. average polarizabilty (αav), chemical hardness (η), electrophilicity index (ω) of some donor–acceptor substituted polychlorinated biphenyl (PCBs) i.e. 2,2′,5,5′-tetrachloro-1,1′-biphenyl (PCB-1a), 2,5,2′,5′-Tetrachloro-4′-dimethylamino-biphenyl-4-carbonitrile (PCB-1b), Dimethyl-(2,5,2′,5′-tetrachloro-4′-nitro-biphenyl-4-yl)-amine (PCB-1c), 3,3′,5,5′-tetrachloro-1,1′-biphenyl (PCB-2a), 3,5,3′,5′-Tetrachloro-4′-dimethylamino-biphenyl-4-carbonitrile (PCB-2b) and Dimethyl-(3,5,3′,5′-tetrachloro-4′-nitro-biphenyl-4-yl)-amine (PCB-2c) were computed along the torsional potential of biphenyl ring. Density functional based hybrid functional CAM-B3LYP with 6-31G(d) basis were used to all the computational study. Out of the six compounds, variation of the global reactivity descriptors e.g. αav, η, ω as a function of torsional angle of biphenyl ring, three compounds are not in conformity with the respective optimum principle i.e. minimum polarizability, maximum hardness and minimum electrophilicity principle. In this present research article, we have raised this issue that apart from electronically stable conformation, localization of π-electron plays a major role in determining the optimum values of global reactivity descriptors, αav, η & ω. On the other hand computation of first average hyper polarizability (βav) as a function of torsional angle shows that the variation of βav are in good agreement with the optical gap as well as electronic spatial extent ( ) of the conformers of all the six compounds.