The beauty of knots at the molecular level

What makes a given object look beautiful to the observer, be it in the macroscopic world or at the molecular level? This very general question will be briefly addressed at the beginning of this essay, in relation to contemporary molecular chemistry and biology, leading to the general statement that, most of the time, beauty is tightly connected to function as well as to the cultural background of the observer. The main topic of the present article will be that of topologically non-trivial molecules or molecular ensembles and the fascination that such species have exerted on molecular or solid state chemists. Molecules with a graph identical to Kuratowski's K₅ or K₃,₃ graphs are indeed highly attractive from an aesthetical viewpoint, but perhaps even more fascinating and beautiful are molecular knots. A general discussion will be devoted to these compounds, which are still considered as exotic species because of the very limited number of efficient synthetic strategies leading to their preparation. Particularly efficient are templated approaches based either on transition metals such as copper(I) or on organic groups able to form hydrogen bonds or acceptor-donor stacks. A particularly noteworthy property of knots, and in particular of the trefoil knot, is their topological chirality. The isolation of both enantiomers of the trefoil knot (3₁) could be achieved and showed that such species have fascinating chiroptical properties. Finally, various routes to more complex and beautiful knots than the trefoil knot, which is the simplest non-trivial knot, will be discussed in line with the remarkable ability of transition metals to gather and orient in a very precise fashion several organic components in their coordination spheres, thus leading to synthetic precursors displaying geometries which are perfectly well adapted to the preparation of the desired knots or links.