Coordination‐Driven Self‐Assembly of a Molecular Knot Comprising Sixteen Crossings

: Molecular knots have become highly attractive to chemists because of their prospective properties in mimicking biomolecules and machines. Only a few examples of molecular knots from the billions tabulated by mathematicians have been realized and molecular knots with more than eight crossings have not been reported to date. We report here the coordination-driven [8+8] self-assembly of a higher-generation molecular knot comprising as many as sixteen crossings. Its solid-state X-ray crystal structure and multinuclear 2D NMR findings confirmed its architecture and topology. The formation of this molecular knot appears to depend on the functionalities and geometries of donor and acceptor in terms of generating appropriate angles and strong π-π interactions supported by hydrophobic effects. This study shows coordination-driven self-assembly offers a powerful potential means of synthesizing more and more complicated molecular knots and of understanding differences between the properties of knotted and unknotted structures.