Synthesis of aromatic liquid crystals with asymmetric diester based on rod-like multi-ring system by two-step esterification method

• Published in: Molecular Crystals and Liquid Crystals 2016-05, Vol.630 (1), p.19-27
• Main Authors: Zheng, Min-Yan, Wei, Yong-Sheng, Geng, Wei, Gu, Yuan-Zi
• Format: Article
• Language: English
• Subjects: Acids; Asymmetric diester; Asymmetry; Benzoic acid; Carboxylic acids; Chemical synthesis; Crystals; Differential scanning calorimetry; esterification; Esters; liquid crystal; Liquid crystals; Mesophase; Molecular chemistry; Texture; the frontier molecular orbitals
• ISSN: 1542-1406; 1563-5287; 1527-1943
• DOI: 10.1080/15421406.2016.1146862

A novel method of two-step esterifications was developed to synthesize compounds with asymmetric double ester groups. By using this method, six rod-like double ester compounds were prepared with p-hydroxy benzaldehyde, p-hydroxy benzoic acid bicyclohexyl carboxylic acid, cyclohexyl benzoic acid and biphenyl carboxylic acid substituted by n-propyl and n-pentyl as main reactants. The structures and properties of target compounds were confirmed by IR, MS, 1 H NMR, elemental analysis, differential scanning calorimetry (DSC) and hot stage polarizing optical microscope (HS-POM). Typical yields of the target molecules were more than 70%. All the molecules have mesophases with the textures of nematic type, indicating a rod-like molecule with a longer rigid skeleton can keep its mesophases. There was no clearing point observed for any of the derivatives before they decomposed so that the temperature ranges of the mesophases could not be determined. The energy differences between frontier molecular orbitals (HOMO-LUMO) (E g ) of the compounds were calculated by cyclic voltammetry (CV). The terminal ring system has an obvious influence on the energy levels and the energy gaps (E g ).