Steric Control over the Threading of Pyrophosphonates with One or Two Cyanostar Macrocycles during Pseudorotaxane Formation

The supramolecular recognition of anions is increasingly harnessed to achieve the self‐assembly of supramolecular architectures, ranging from cages and polymers to (pseudo)rotaxanes. The cyanostar (CS) macrocycle has previously been shown to form 2 : 1 complexes with organophosphate anions that can be turned into [3]rotaxanes by stoppering. Here we achieved steric control over the assembly of pseudorotaxanes comprising the cyanostar macrocycle and a thread that is based, for the first time, on organo‐pyrophosphonates. Subtle differences in steric bulk on the threads allowed formation of either [3]pseudorotaxanes or [2]pseudorotaxanes. We demonstrate that the threading kinetics are governed by the steric demand of the organo‐pyrophosphonates and in one case, slows down to the timescale of minutes. Calculations show that the dianions are sterically offset inside the macrocycles. Our findings broaden the scope of cyanostar‐anion assemblies and may have relevance for the design of molecular machines whose directionality is a result of relatively slow slipping. Control over the binding stoichiometry and the threading kinetics is achieved in pseudorotaxanes comprising the anion‐binding cyanostar macrocycle and organic pyrophosphonates with fine‐tuned steric bulk. The approach allowed the selective assembly of [3]pseudorotaxanes and [2]pseudorotaxanes, and it provided insights that are valuable for future work on anion recognition and the design of molecular machines.