The Role of the 1,2,3-Triazolyl Heterocycle in the Helical Columnar Assembly and Electric Field Response

Abstract

Here, we have proven the role of the 1,2,3-triazolyl group in the helical assembly and electric field (E-field) response upon comparing liquid crystal analogs 1 and 2 based on 1,2,3triazolyl and 1,3,4-oxadiazolyl linkers, respectively. An ordered helical column was only observed in 1, driven by the hydrogen-bonding interactions between the adjacent triazolyl nitrogen and hydrogen atoms. X-ray diffraction and energy simulations indicate that the helical column is a 11 2 helix and the helical axis does not coincide with the center of the molecular long axis. The key for the formation of the helical column is the tilted conformation of 1 originating from the steric repulsion between the triazolyl C−H and C−H of the aromatic core. Analysis of the dynamics in the simple hexagonal columnar phase revealed that the in-plane rotational motion of the triazolyl linker (1) is allowed, while the oxadiazolyl linker of 2 has limited conformational flexibility. A uniform alignment under an E-field only occurs in 1, demonstrating the requirement for conformational flexibility in the polar linker. This alignment enhances the electric conductance of 1 by approximately two-fold.