Development of a Fluorescent Nanofibrous Template by in Situ SNAr Polymerization of Fluorine-Containing Terphenyls with Aliphatic Diols: Self-Assembly and Optical and Liquid Crystal Properties

Abstract

Stimulus-responsive supramolecular organogels have been broadly studied, but the assembly of a liquid crystalline organogel with a thermoreversible response remains a challenge. This could be attributed to the difficulty of designing organogelators with liquid crystalline properties. Nucleophilic aromatic substitution (SNAr) has been utilized to produce a diversity of pentafluorobenzene-containing aromatics, which are very regioselective to para positions. Those pentafluorobenzene-functionalized aromatics have been ideal compounds for the preparation of calamitic liquid crystals. In this context, novel fluoroterphenyl-containing main-chain polyether (FTP@PE) was synthesized using in situ SNAr polymerization as a convenient and effective synthetic strategy toward the development of fluorescent liquid crystals bearing fluoroterphenyl and ether groups. The fluoroterphenyl unit was synthesized by Cu(I)-supported decarboxylation cross-coupling of potassium pentafluorobenzoate and 1,4-diiodobenzene. The chemical structures of FTP@PE were studied with 1H/13C/19F nuclear magnetic resonance and infrared spectra. The liquid crystal mesophases were determined with differential scanning calorimetry and polarizing optical microscopy. Ultraviolet–visible absorbance and emission spectral profiles showed solvatochromic activity. The nanofibrous morphologies were studied with a scanning electron microscope. The organogels of FTP@PE were developed in a number of solvents via van der Waals attraction forces of aliphatic moieties and π stacking of fluoroterphenyl groups. They demonstrated thermoreversible responsiveness.