Synthesis, characterisation and mesomorphic properties of a homologous series of oxovanadium(iv) complexes containing a bidentate [N,O] donor Schiff base mesogen

Abstract

A series of oxovanadium(iv) complexes of the type [VO(L)2], [L = N-(4-n-alkoxysalicylaldimine)-4-hexadecyloxyaniline, n = 8, 10, 12, 14, 16 or 18] have been synthesised and characterised by FT–IR, ¹H NMR, ¹³CNMR, UV–Vis, and FAB mass and magnetic susceptibility measurements. The ligands are coordinated to the vanadyl ion in a bidentate fashion. The mesomorphic behaviour of the ligands and their vanadyl complexes was investigated by polarising optical microscopy and differential scanning calorimetry. The compounds were all highly thermally stable, and their mesomorphic properties were found to depend on the length of the carbon chain. Both the ligands and their higher homologue complexes exhibited a SmC mesophase. In the case of the lower homologues the ligands exhibited the SmC phase but their complexes a SmA mesophase. The mesophase–isotropic transition temperatures for the complexes were significantly higher than those of the ligands. Variable temperature magnetic susceptibility measurements on the vanadyl complexes clearly suggested absence of any exchange interactions among the vanadyl spin centres. Cyclic voltammetry showed a quasi-reversible one-electron response at 0.51 V for the VO(iv)–VO(v) redox couple. Density functional theory studies carried out using DMol3 at the BLYP/DNP level to determine the energy-optimised structure revealed a distorted square pyramidal geometry for the vanadyl complexes, with the alkoxy tails projecting away from one another.

Keywords:

• metallomesogen
• vanadium
• smectic mesomorphism
• density functional theory
• electrochemistry

Acknowledgements

The authors wish to thank SAIF, NEHU and CDRI, Lucknow for analytical and spectral data. GD is grateful for financial support from DST and UGC, Government of India. The computational resources provided by Dr R.C. Deka, Tezpur University, India, are also acknowledged.