Knotting and Threading of Molecules: Chemistry and Chirality of Molecular Knots and Their Assemblies

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Abstract
How and why do molecules tangle or thread? Investigations of molecular knots (knotanes) may shed some light on the mechanisms of (supra)molecular templation and the folding of molecules that result in intertwining. The topological chirality of these fascinating molecules leads to new types of isomerism and paves the way to nanosized molecular motors. Their preparation and derivatization makes high demands on modern synthetic methods and analytical separation since molecular knots are formed in a more or less planned design based on metal coordination or hydrogen‐bonding patterns. This Review describes the development of templation techniques for the synthesis of knotanes and their chiral resolution as well as their selective functionalization and use as building blocks in the synthesis of higher knotane assemblies. Such assemblies can possess linear, branched, or even macrocyclic structures which, on the one hand, introduce unprecedented isomeric compositions that arise from multiple topological stereogenic units and, on the other, define new types of artificial macromolecules beyond polymers and dendritic species.

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