Successive Sulfur Oxidation Directs Topological Transformation From 4 ₁ Knot to 632$6_3^2$ Link

Abstract

Abstract Achieving transformation between different types of topologies remains a challenge in supramolecular chemistry. Herein, sulfur oxidation was utilized as the stimuli to trigger topological transformations from knots to links. The process began with a thioether‐type precursor, M (4 1 metallic knot), which was synthesized by self‐assembling the sulfur‐bridged ligand L with building block B in high yield. Following oxidation reactions, we successfully transformed the octanuclear 4 1 metallic knot ( M ) with four crossing points into a sulfoxide‐type dodecanuclear metallic link ( M‐O ) with six crossing points as an intermediate product, and then to a sulfone‐type dodecanuclear metallic link ( M‐2O ) with six crossing points, which achieves a dual leap in both metal nuclearity and crossing complexity. Remarkably, the key to the transformation lies in using the embedded S‐centres of M as molecular triggers and stepwise oxidation (‐S‐→‐S(O)‐→‐S(O) 2 ‐) enabled precise modulation of the geometric configuration of the sp 3 S‐centres, drastically altering the range of accessible coordination vectors and inducing conformational self‐adaptation among components. This strategy establishes a novel oxidation‐mediated interconversion paradigm among complex topologies, offering new insights for designing dynamic molecular triggers in intelligent material systems.