Unconventional assemblies of bisacylhydrazones: The role of water for circularly polarized luminescence

Abstract

Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoelectronic materials, including materials displaying high-performance circularly polarized luminescence (CPL). Herein, we report the first chiral supramolecular polymer systems based on hydrazone–pyridinium conjugates comprising alkyl chains of different lengths, which afforded control of the apparent supramolecular chirality. Although supramolecular chirality is governed basically by the remote chiral centers of alkyl chains, helicity inversion was achieved by controlling the conditions under which the hydrazone building blocks underwent aggregation (i.e., solvent compositions or temperature). More importantly, the addition of water to the system led to aggregation-induced hydrazone deprotonation, which resulted in a completely different self-assembly behavior. Structural water molecules played an essential role, forming the assembly's channel-like backbone, around which hydrazone molecules gathered as a result of hydrogen bonding interactions. Further co-assembly of an achiral hydrazone luminophore with the given supramolecular polymer system allowed the fabrication of a novel CPL-active hydrazone-based material exhibiting a high maximum value for the photoluminescence dissymmetry factor of −2.6 × 10−2.