Selective synthesis and structural transformation between a molecular ring-in-ring architecture and an abnormal trefoil knot

The synthesis of complicated supramolecular architectures and the study of their reversible structural transformations remains a fascinating challenge in the field of supramolecular chemistry. Herein, two types of novel coordination compounds, a non-intertwined ring-in-ring assembly and an abnormal trefoil knot were constructed from a strategically selected Cp*Rh building block and a semi-rigid N,N′-bis(4-pyridylmethyl)diphthalic diimide ligand via coordination-driven self-assembly. Remarkably, the reversible transformation between the abnormal trefoil knot and the ring-in-ring assembly or the corresponding tetranuclear macrocycle could be achieved by the synergistic effects of Ag(+) ion coordination and alteration of the solvent. Single-crystal X-ray crystallographic data and NMR spectroscopic experiments support the structural assignments.