Application of periodic density functional theory calculations for exploring copper(II) coordination effects on the mesophase behavior of p-n-alkoxybenzoic acids

Abstract

Copper(II) benzoates ([Formula: see text]OBA-Cu) with various terminal alkoxy carbon numbers, [Formula: see text]–12, were prepared from [Formula: see text]-[Formula: see text]-alkoxy benzoic acids (nOBAs). Fourier transform infrared (IR) experiments suggested that dimerization through copper(II) chelating bidentate coordination created [Formula: see text]OBA-Cu with a linear rod-like structure, similar to the hydrogen-bonded structure of its parent [Formula: see text]OBA. However, the coordination structure of [Formula: see text]OBA-Cu changed during heating. Periodic density functional theory calculations provided valuable insight into the possible arrangement of the parent and copper(II)-coordinated [Formula: see text]OBAs. The formation of binuclear complexes between two adjacent [Formula: see text]OBA-Cu dimers forced [Formula: see text]OBA-Cu to arrange itself in a layer and exhibit smectic A mesophase. Accordingly, four types of IR stretching absorption of benzoyl carbonyl were observed in binuclear [Formula: see text]OBA-Cu complexes, replacing the original symmetric and asymmetric vibrations of benzoyl carboxylate in chelating bidentate coordination. The lateral association by [Formula: see text]–[Formula: see text] interactions between adjacent parent [Formula: see text]OBA dimers preferred a progressive smectic C arrangement. The origin of the odd–even effect was understood from the consideration of the molecular structure.