A molecular meccano kit

A range of secondary dialkylammonium (R2NH2+) ions has been shown to thread through the cavities of appropriately-sized crown ether compounds to afford interwoven complexes. X-Ray crystallographic investigations to probe the solid-state properties of these supermolecules have revealed that many subtle factors-e.g., solvent of crystallisation, crown ether conformation and anion interactions-can influence the nature of the overall three-dimensional superstructures. Nonetheless, a family of building blocks-namely R2NH2+ ions and crown ethers-can be generated, which constitute a molecular meccano kit. By mixing and matching these modules in different ways, intricate interwoven supramolecular architectures can be constructed. From relatively simple beginnings-where one R2NH2+ ion is threaded through one monotopic crown ether (dibenzo[24]crown-8)-the designed evolution of the building blocks in the molecular meccano kit has led to more elaborate multiply encircled and/or multiply threaded superstructures. The effects of crown ether constitution, macroring size, and both crown ether as well as R2NH2+ ion substitution, upon the solid-state behaviour of these interwoven complexes have also been examined. A statistical analysis of the hydrogen bonding interactions observed in these systems has been carried out. It reveals that a reasonable correlation exists between N+-H . . .O bond angle and H . . .O bond length. The correlation between C-H . . .O bond angle and H . . .O distance is poor, suggesting that C-H . . .O hydrogen bonding interactions are of secondary importance in determining the co-conformations adopted by these supermolecules.