Synthesis, Structural and Theoretical Analyses of C≡N···I Halogen-Bonded Liquid Crystalline Complexes of 4-Cyano-4′-alkoxy Biphenyl Systems

Abstract

A series of 4-cyano-4′-alkoxybiphenyl compounds were synthesized by varying the spacer chain lengths (−CH2−)n, where n = 3–10, for the systematic study of a halogen-bonded (XB) complex with 1,4-diiodotetrafluoro benzene. The XB liquid crystalline complexes obtained from the liquid-assisted grinding method were characterized by FTIR, Raman, DSC, and PXRD studies. Further, C≡N···I XB interaction was established by single-crystal X-ray diffraction analysis. The odd-even analysis has suggested that the even carbon chain length containing XB liquid crystalline complexes shows slightly higher alteration in their isotropic temperature compared to the odd carbon chain lengths of such complexes. Furthermore, it is interesting to note that the higher alkyl chain complexes (n = 6–10) showed liquid crystalline temperature at lower values with respect to their ligands. The Hirshfeld and energy framework analyses have also been carried out to assess the stability and percentage contribution of XB noncovalent interaction. The frontier molecular orbital, noncovalent interaction, molecular electrostatic potential, and QTAIM analysis were performed using DFT to evaluate the nature of XB in these halogen-bonded liquid crystalline systems.