Donor (D)-Acceptor (A) Type Supramolecular Organogelators with Crown Ether-Annulated Tetrathiafulvalene-Pyridazine Conjugates.

T-shaped π-conjugated molecules based on the crown ether-annulated tetrathiafulvalene (TTF)-pyridazine skeleton were prepared, and their gel-forming capacities in various organic solvents were evaluated. The two gelators carrying C14 and C16 alkyl chain units (1b and 1c) displayed efficient gelation in aromatic, polar, and nonpolar solvents owing to the introduced crown ether residue. Stimuli-responsive properties, including temperature sensitivity, redox activity, anion responsiveness, and Na+-dependent behavior, were exhibited by the synthesized gel. Notably, the organogelators easily generated stable charge-transfer complex-based organic gels with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (T4CNQ) and iodine (I2). In addition, they also showed interaction with a fullerene in toluene system, leading to the formation of a binary gel. Meanwhile, according to scanning electron microscopic (SEM) observation, the xerogels revealed the construction of one-dimensional (1D) helical fibers, two-dimensional (2D) ribbons, and helical ribbons. According to small-angle X-ray scattering (SAXS) analysis results, it was confirmed that the molecules maintained a hexagonal columnar packing structure in the gel phase. These results showed that stacking of columnar tetrathiafulvalene (TTF)-pyridazine cores in the fiber or ribbon provides an efficient pathway for electron conduction.