1D materials from ionic self-assembly in mixtures containing chromonic liquid crystal mesogens.

Abstract

Ionic self-assembly is a simple yet powerful method to obtain robust nanostructures. Herewith, we use mixtures of oppositely-charged porphyrins that can act as mesogens to form chromonic liquid crystals in water, i.e., molecular stacks with orientational (nematic) or positional (hexagonal) order. Electrostatic locking coupled with π-π interactions between aromatic groups within the stacks, together with inter-stack hydrogen bonding induce formation of all-organic crystalline nanofibers with high aspect ratio (a few tenths of nanometers in width but several tenths of micrometers in length) and that display branching. The nanofibers prepared from metal-free porphyrin units feature interesting optical properties, including an absorption spectrum that is different from the simple sum of the individual spectra of the components, which is attributed to a striking aggregation-induced chromism. When in contact with some polar organic solvents the materials become fluorescent, as a result of disaggregation. In a proof-of-concept, the obtained self-assembled one-dimensional (1D) materials were carbonized (yield ca. 60%) to produce nitrogen-doped carbon nanofibers that can be used as active electrode materials for energy storage applications.