Supramolecular nanostructures constructed by rod–coil molecular isomers: effect of rod sequences on molecular assembly

Abstract

Coil–rod–coil molecules, composed of flexible oligoether chains and conjugated rod blocks, have a well-known ability to produce various nanostructures in bulk and in aqueous solution. Herein we report the synthesis and self-assembly of coil–rod–coil molecules based on the sequence of the rod building block and the type of oligoether coil chain. These molecules consist of conjugated rod segments, which are composed of biphenyl, terphenyl, and acetylenic bonds, with chiral oligoether chains as flexible coil segments. The experimental results imply that the sequence of the rod segments markedly influences the self-assembled nanostructures of coil–rod–coil molecules in the bulk state, and that the type of coil chain strongly affects the morphology of the supramolecular nanoassemblies of these molecules in aqueous solution. In the bulk state, molecules 1a and 1b, which contain biphenyl units connected to the end of the coil segments self-organize into a hexagonal perforated lamellar phase, and oblique columnar and body-centred tetragonal structures, respectively. However, molecules 2a and 2b bearing terphenyl units linked to the end of the coil segments self-assemble into lamellar, hexagonal perforated lamellar and hexagonal columnar structures. In aqueous solution, rod–coil molecular isomers with linear chiral oligoether chains self-assemble into helical nanofibres of various lengths. Meanwhile, isomers with chiral oligoether dendron chains self-organize into sheet-like nanoribbons of different sizes.