Phase Behavior and DFT Calculations of Laterally Methyl Supramolecular Hydrogen-Bonding Complexes

Four new series of laterally methyl-substituted hydrogen-bonded supramolecular complexes were prepared. The prepared complexes were thermally investigated by differential scanning calorimetry (DSC) and phases identified by polarized light microscopy (PLM). Supramolecular hydrogen-bonded complexes formed from a 1:1 mixture of any two derivatives, bearing different alkoxy chains, of 4-alkoxyphenylazobenzoic acid and 4-(2-(pyridin-4-yl)diazenyl-(2-(or 3-)methylphenyl) 4-alkoxybenzoate. The investigated 1:1 mixture made by introducing a lateral methyl group by different spatial orientation angles into pyridine-based components. All new complexes were confirmed by Fourier-transform infrared spectroscopy (FTIR) and computational calculations used to study their stabilities. It is found that the prepared complexes are dimorphic, exhibiting smectic C and enhanced nematic phases. A comparison was made between the new series and previously investigated simpler complexes, revealed that the incorporation of the phenylazo group elongate the mesogenic part and hence broad nematic phases were obtained with high stability.