Assembly of a self-complementary monomer: formation of supramolecular polymer networks and responsive gels

Self-complementary monomer 1, which combines a macrotricyclic polyether and two dibenzylammonium ions together, was synthesized, and its self-assembly into supramolecular polymer networks by host-guest interactions was studied. For the purpose of comparative study, two model molecules 2 and 3 were also prepared. It was found that model molecule 2 and dibenzylammonium ion 4 form a 1:2 complex in solution and in the solid state, which afforded a model system for the investigation of the assembly behavior of monomer 1. Consequently, the (1)H NMR spectrum of 1 in CD(3)CN showed characteristic proton signals similar to the model system, which suggested that 1 self-assembles into a supramolecular polymer network. Formation of the supramolecular polymer was further evidenced by the MALDI-TOF MS spectrum, viscometry, and dynamic light-scattering (DLS) experiments. Moreover, it was found that the decomposition and re-formation of the supramolecular polymer could be chemically controlled by the use of triethylamine and trifluoroacetic acid. Interestingly, the supramolecular polymer forms an organogel both in CD(3)CN and in 1:1 (v/v) CDCl(3)/CD(3)CN, and reversible thermo- and pH-induced gel-sol transitions were also found. The presented work will provide a new strategy for the construction of supramolecular polymers with specific structures and properties.