Self-Assembly of Molecular Figure-Eight Knots Induced by Quadruple Stacking Interactions

Molecular figure-eight knot (notation: 4₁) is extremely rare and presents great synthetic challenge due to its essentially complicated entanglement. To solve this synthetic problem, a quadruple stacking strategy was developed. Herein, we report the efficient self-assembly of figure-eight knots induced by quadruple stacking interactions, through the combination of four carefully selected naphthalenediimide (NDI)-based pyridyl ligands and Cp*Rh building blocks bearing large conjugated planes in a single-step strategy. Notably, slight size adjustment of the Cp*Rh units was found to affect the stability of the figure-eight knots in methanol. Additionally, reversible structural transformations between these figure-eight knots and corresponding metallorectangles could be achieved by concentration changes and solvent- and guest-induced effects. X-ray crystallographic data and NMR spectroscopy provide full confirmation of these phenomena.