Helic[1]triptycene[3]arene: Synthesis, Complexation, and Formation of [2]Rotaxane Shuttle

A new macrocyclic arene, helic[1]triptycene[3]arene H, was conveniently synthesized in 37% yield by a one-pot reaction starting from 2,6-dimethoxyl-3,7-dihydroxymethyltriptycene. Macrocycle H showed fixed conformation in solution and could form 1:1 complexes with a series of neutral guests, secondary ammonium salts, and tertiary ammonium salts in both solution and solid states. The association constants between H and the neutral guests were between (1.23 ± 0.10) × 10² and (4.70 ± 0.47) × 10³ M^-1, while the association constants between H and the ammonium guests were between (1.35 ± 0.12) × 10³ and (1.59 ± 0.14) × 10⁵ M^-1. Moreover, H showed bigger association constants with secondary ammonium salts than those with tertiary ammonium salts possibly because of the steric hindrance effect and multiple intermolecular interactions. The stimuli-responsive complexation between H and the ammonium salts could be controlled by the addition and removal of acids and bases as well. Based on the host-guest complexation between H and the secondary ammonium salt, [2]rotaxane was further synthesized, and its shuttling motion could be efficiently controlled by an acid and base.