An abnormal O-coordinated zwitterionic ligand L was designed and applied to construct intricate supramolecular elements based on half-sandwich Cp*Rh units. This zwitterionic ligand has two stable conformations, C- and Z-shapes, which undergo self-adaptation when assembled with different building blocks. Two trefoil knots were obtained using dinuclear building blocks (Cp*Rh)2(1,4-DHATQ)(OTf)2 and (Cp*Rh)2(DHNAD)(OTf)2, in which the ligand L was observed to adopt its C-shaped conformation. In addition, two novel one-dimensional chains were constructed using the building blocks (Cp*Rh)2(1,5-DHATQ)(OTf)2 and (Cp*Rh)2(DHNTQ)(OTf)2. Only the Z-shaped conformation of ligand L was observed in these two 1D chains.
