Interwoven supramolecular arrays via the noncovalent polymerization of pseudorotaxanes

This review describes how the noncovalent polymerization of pseudorotaxanes - inclusion complexes in which thread-like molecules or ions interpenetrate macrorings' central cavities without the formation of a mechanical bond - leads to the production of interwoven supramolecular arrays in the solid state. The noncovalent synthesis of these polymeric supramolecular architectures requires the independent and simultaneous operation of at least two different orthogonal recognition algorithms, viz. a threading algorithm, for the formation of the pseudorotaxane, and a noncovalent polymerization algorithm, that permits interpseudorotaxane association in the crystal. The information required for the operation of these orthogonal recognition algorithms is preprogrammed into the covalent frameworks of the interwoven supramolecular arrays' precursors. Several different types of intermolecular interactions have been employed by crystal engineers for the noncovalent synthesis of interwoven supramolecular arrays in the solid state, in particular, metal-ligand, π-π stacking and hydrogen bonding interactions.