Integrative, Orientational Self‐Sorting at the Four‐Crossing Level in Molecular Knots and Links

Low-symmetry mechanically interlocked molecules (MIMs) remain challenging targets because of their anisotropic structures and synthetic complexity. We devised a self-sorting strategy employing two unsymmetric flexible bidentate ligands, L^ab and L^cd, which co-assemble with two size-differentiated rigid chelating building blocks and half-sandwich organometallic units. This approach yields three discrete topologies with high orientational fidelity: a Solomon link ( <mml:math x