Gel Formed by Self-Assembly of a Urea-Modified Monopyrrolotetrathiafulvalene Derivative Displays Multi-Stimuli Responsiveness and Absorption of Rhodamine B.

ABSTRACT

A new monopyrrolotetrathiafulvalene-based derivative containing a urea group was designed, synthesized and thoroughly characterized. It proved to be a non-gelator in a single solvent even when heated or sonicated. However, it could self-assemble in a CHCl3 (CH2 Cl2 )/n-hexane mixture to form a thermo-responsive supramolecular organogel. SEM, FT-IR spectroscopy, UV/Vis absorption spectroscopy, and SAXS revealed that in the organogel system, the gelators self-assembled into supramolecular networks with a J-type aggregation mode under the joint effect of π-π stacking, intermolecular hydrogen-bonding, and van der Waals forces. Interestingly, the gel phase was shown to undergo reversible gel-sol transformation induced by Fe3+ -Vitamin C (Vc), trifluoroacetic acid-triethylamine (TFA-TEA) and picric acid (PA)-NaOH. In particular, in the presence of picric acid, the experimental results proposed that charge transfer occurred from the electron-donor gelator to the electron-acceptor picric acid due to the possibility of complex formation. Furthermore, the formed organogel could behave as the matrix for encapsulating cationic fluorescent dye from wastewater, and the adsorption efficiency was directly proportional to the concentration of the gelator.