Construction of supramolecular nanostructures from v-shaped amphiphilic rod-coil molecules incorporating phenazine units

Abstract

A series of bent-shaped molecules, consisting of dibenzo[a,c]phenazine and phenyl groups connected together as a rod segment, and poly(ethylene oxide) (PEO) with a degree of polymerization (DP) of 6 as the coil segment, were synthesized. The self-assembling behavior of these molecules by differential scanning calorimetry (DSC), thermal optical polarized microscopy (POM), small-angle X-ray scattering spectroscopy (SAXS), atomic force microscopy (AFM), and transmission electron microscopy (TEM), revealed that carboxyl or butoxy carbonyl groups at the 11 position of dibenzo[a,c]phenazine noticeably influence self-organization of molecules into supramolecular aggregates in bulk and aqueous solutions. Molecules 1 and 2 with chiral or non-chiral PEO coil chains and the carboxyl group at the rod segments self-organize into a hexagonal perforated lamellar structure and a hexagonal columnar structure in the solid state. In aqueous solution, molecules 1 and 2 self-assemble into diverse lengths of nanofibers, whereas molecules 3 and 4 with butoxy carbonyl groups exhibit a self-organizing capacity to form diverse sizes of spherical aggregates.