For the Occasion of Japan Society of Coordination Chemistry International Award: Metal Coordination as a Template Strategy to Make Resilient Woven Materials

Transition metal ions as a template method has been widely used in the field of supramolecular chemistry. The metal complexation is advantageous in making complex supramocluar architectures because it pre-organizes the ligands into a desirable orientation which faciliatates the following ring-closing reaction, with shorter synthetic steps and generally higher yield. In a similar fashion, this synthetic strategy has recently been adopted to make extended materials by linking the metal-coordinated building blocks with design principles of reticular synthesis. Individual building units are stitched together through strong covalent bond formation to yield long covalent molecular threads that are woven two- or three-dimensionally (2D or 3D), at regular intervals templated by the metal ions. For example, by linking functionalized tetrahedrally-shaped metal complexes with linear links through reversible imine bond formation, crystalline 3D covalent organic frameworks with diamond topology, COF-505 and COF-112, have been constructed by design. In particular, the metal templates can be post-synthetically removed so that the threads have high degrees of freedom to move in respect to each other, which leads to unusal mechanical properties of the woven materials.