Intriguing π-interactions involving aromatic neutrals, aromatic cations and semiconducting behavior in a pyridinium-carboxylate salt

Abstract

A new pyridinium-carboxylate salt (1) has been synthesized and characterized by elemental analysis, spectroscopy, electrical studies, and single-crystal X-ray diffraction. X-ray structure of 4,4′-oxybis(benzoic acid) with 4-(Dimethylamino)pyridine is stabilized through hydrogen bonds, C‒H···π, and numerous π-interactions together with π···π, π···π+, and π+···π+stacking. The cooperativity of the weak noncovalent interactions has been explored well that plays a crucial role in building diverse extended supramolecular frameworks. The hydrogen bonds dictate the basic structural motifs representing the supramolecular association. However, the cooperativity of the weak noncovalent contacts plays a significant role in constructing the final solid-state structure. The entire assembly produces a rare combination of π···π/π···π+/π+···π+/π+···π extended network. The binding energies of the noncovalent interactions have anticipated the usage of DFT calculations. Intricate combinations of these noncovalent interactions are characterized through computational studies by using Bader's theory of “Atoms-in-Molecules” (AIM) and “noncovalent interaction” (NCI) plot index. The evaluation of topological parameters at (3, -1) BCPs ensured the ‘closed-shell’ nature of the intermolecular interactions. By employing Tauc's plot, the optical band gap was calculated from UV–Vis spectroscopy. A device was fabricated for the analysis of I-V characteristics of the compound. An impedance study was carried out and consequently, Nyquist plot was represented for the further investigation of the semiconducting behavior of the compound.