Polycatenanes Formed of Self‐Assembled Metal Organic Cages

Abstract Poly‐[n]‐catenanes (PCs) self‐assembled of three‐dimensional (3D) metal organic cages (MOCs) (hereafter referred to as PCs‐MOCs) are a relatively new class of mechanically interlocked molecules (MIMs) that combine the properties of MOCs and polymers. The synthesis of PCs‐MOCs is challenging because of the difficulties associated with interlocking MOCs, the occurrence of multiple weak supramolecular electrostatic interactions between cages, and the importance of solvent templating effects. The high density of mechanical bonds interlocking the MOCs endows the MOCs with mechanical and physical properties such as enhanced stability, responsive dynamic behavior and low solubility, which can unlock new functional properties. In this Minireview, we highlight the benefit of interlocking MOCs in the formation of PCs‐MOCs structures as well as the synthetic approaches exploited in their preparation, from thermodynamic to kinetic methods, both in the solution and solid‐states. Examples of PCs‐MOCs self‐assembled from various types of nanosized cages (i.e., tetrahedral, trigonal prismatic, octahedral and icosahedral) are described in this article, providing an overview of the research carried out in this area. The focus is on the structure–property relationship with examples of functional applications such as electron conductivity, X‐ray attenuation, gas adsorption and molecular sensing. We believe that the structural and functional aspects of the reviewed PCs‐MOCs will attract chemists in this research field with great potential as new functional materials in nanotechnological disciplines such as gas adsorption, sensing and photophysical properties such as X‐ray attenuation or electron conductivity.