Lamellar columnar liquid-crystalline mesophases as a 2D platform for anhydrous proton conduction

Abstract

Several series of dihalide Pd(II) compounds bearing pyridyl or isoquinolinylpyrazole ligands have been strategically designed and synthesised to exhibit columnar mesomorphism in wide stability ranges. The coordination of the pyrazoles to the fragments PdX_2 (X = Cl, Br, I) generates half-disc molecules that are capable of self-assembling into discotic dimers via intermolecular interactions. This disc-like shape is required for the supramolecular organisation of the lamellar columnar mesophases, which are formed at temperatures below 100 ºC in most cases. It was found that these metallomesogens behave as 2D proton conducting materials under anhydrous conditions. The high fluidity properties of the mesophase facilitate proton conduction as a result of the spontaneous dissociation of the acidic pyrazole proton at the melting temperature. For the first time, lamellar columnar mesophases are demonstrated to serve as a 2D platform to induce water-free proton conductivity in dihalide Pd(ii) metallomesogens.