A molecular machine directs the synthesis of a catenane

Precise mechanical manipulation of molecules is inherently difficult owing to random thermal motion. Although directed movement on the molecular scale has been achieved, using it to impose specific-especially energetically disfavored-shapes on molecules and construct mechanically interlocked structures remains a fundamental challenge. In this study, we report the synthesis of a catenane enabled by a molecular motor that winds molecular strands into discrete entangled structures, each defined by a specific number of mechanical crossings. Light energy drives unidirectional motor rotation, enabling path-dependent control over a sequence of thermodynamically disfavored yet mechanically distinct and kinetically stable winding states, which are covalently captured and subsequently released to yield a catenane. This machine-directed approach offers a general proof-of-concept strategy for the template-free construction of mechanically interlocked molecules.