An Investigation of Five Component [3+2] Self-Assembled Cage Formation Using Amidinium···Carboxylate Hydrogen Bonds

Abstract

The assembly of hydrogen bonded cages using amidinium···carboxylate hydrogen bonding interactions was investigated. A new tris-amidinium hydrogen bond donor tecton based on a tetraphenylmethane scaffold was prepared and its self-assembly with the terephthalate anion studied, and a new tricarboxylate hydrogen bond acceptor tecton was synthesised and its assembly with the 1,3-benzenebis(amidinium) hydrogen bond donor explored. In both cases, molecular modelling indicated that the formation of the cages was geometrically feasible and 1H NMR spectroscopic evidence was consistent with interactions between the components in competitive d6-DMSO solvent mixtures. DOSY NMR spectroscopy of both systems indicated that both components diffuse at the same rate as each other, and diffusion coefficients were consistent with cage formation, and with the formation of assemblies significantly larger than the individual components. An X-ray crystal structure showed that one of the assemblies did not have the desired cage structure in the solid state.