Supramolecular ionic networks with superior thermal and transport properties based on novel delocalized di-anionic compounds

Supramolecular ionic networks based on highly delocalized dianions having (trifluoromethane-sulfonyl)imide, (propylsulfonyl)methanide and (cyano-propylsulfonyl)imide groups were developed and their physical properties were examined in detail. Most of the synthesized compounds were semi-crystalline possessing Tm values close to 100°C; however, amorphous networks were also obtained using aromatic asymmetric dianions. Rheological measurements in temperature sweep tests at a constant frequency confirmed two different behaviors: a fast melting close to the Tm for semi-crystalline materials and a thermoreversible network for liquid transition for the amorphous supramolecular ionic networks. It was found that the amorphous ionic networks showed significantly higher ionic conductivity (10^-3 S cm^-1 at 100°C) than the crystalline ionic networks (10^-6 S cm^-1) and previously reported amorphous citrate ionic networks (10^-5 S cm^-1). The supramolecular ionic networks containing hydrophobic (trifluoromethanesulfonyl)imide groups demonstrated improved water stability and higher thermal stability than the previously synthesized carboxylate ones. Noticeably, the obtained amorphous supramolecular ionic networks combine not only high ionic conductivity and thermal stability, but also self-healing properties into the same material.

Controlling the supramolecular architecture of molecular gels with surfactants

Manipulating molecular assembly is significant for achieving materials with desirable performances. In this paper, two nonionic surfactants, Span 20 and Triton X-100, are used to tune the nucleation and fiber growth of a molecular gelator 2,3-di-n-decyloxyanthracene (DDOA). Confocal microscopic images show that Span 20 induces elongation of DDOA spherulites, and promotes fiber side branching. In contrast, Triton X-100 enhances the primary nucleation of DDOA leading to the formation of smaller DDOA spherulites, and promotes fiber tip branching. (1)H NMR investigation demonstrates strong interactions between the hydrophobic tails of the surfactants and the alkyl chains of DDOA molecules.The interactions significantly reduce the diffusion of DDOA molecules. The different effects of the two surfactants could be attributable to their different alkyl hydrophobic tails. The hydrophobic tail of Span 20 is similar to the alkyl chain of DDOA, which could promote the adsorption of Span 20 on the fiber side surface rich in alkyl chains of DDOA.While the benzene ring in the hydrophobic tail of Triton X-100 could facilitate the primary nucleation of DDOA and the adsorpion of Triton X-100 on the fiber tip surface rich in aromatic structure of DDOA. The observations of this work will help the development of a convenient approach to tune the fiber network structure of molecular gels.