Recent developments in the construction of metallacycle/metallacage-cored supramolecular polymers via hierarchical self-assembly.

Supramolecular polymers have received considerable attention during the last few decades due to their scientific value in polymer chemistry and profound implications for future developments of advanced materials. Discrete supramolecular coordination complexes (SCCs) with well-defined size, shape, and geometry have been widely employed to construct hierarchical systems by coordination-driven self-assembly with the spontaneous formation of metal-ligand bonds, which results in the formation of well-defined two-dimensional (2D) metallacycles or three-dimensional (3D) metallacages with high functionalities. The incorporation of discrete SCCs into supramolecular polymers by the orthogonal combination of metal-ligand coordination and other noncovalent interactions or covalent bonding could further facilitate the construction of novel supramolecular polymers with hierarchical architectures and multiple functions including controllable uptake and release of guest molecules, providing a flexible platform for the development of smart materials. In this review, the recent progress in metallacycle/metallacage-cored supramolecular polymers that were constructed by the combination of metal-ligand interactions and other orthogonal interactions (including hydrophobic or hydrophilic interactions, hydrogen bonding, van der Waals forces, π-π stacking, electrostatic interactions, host-guest interactions and covalent bonding) has been discussed. In addition, the potential applications of metallacycle/metallacage-cored supramolecular polymers in the areas of light emitting, sensing, bio-imaging, delivery and release, etc., are also presented.