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.