Solvent-Dependent Self-Assembly of a Pillar[5]arene-Based Poly-Pseudo-Rotaxane Linked and Threaded by Silver(I)...

In the supramolecule area, the fabrication of a new concept called polyrotaxanes or poly-pseudo-rotaxanes remains challenging. We herein report the formation of a poly-pseudo-rotaxane in which the same salt-type guest serves both linking and threading in the resulting structure. The combination of A1/A2-thiopyridyl pillar[5]arene (L) and silver(I) trifluoroacetate in CHCl₃/CH₃OH afforded a one-dimensional (1D) poly-pseudo-rotaxane. In this structure, to our surprise, the AgCF₃CO₂ guest not only links the di-armed L ligands via an infinite -L-Ag-L-Ag- arrangement but also threads into a pillar[5]arene cavity in a dimer form, (AgCF₃CO₂)₂. In contrast, the same reaction in CH₂Cl₂/CH₃OH yielded a simple 1D coordination polymer because an included CH₂Cl₂ molecule in the pillar[5]arene cavity prevents the threading of the silver(I) trifluoroacetate guest. Comparative ¹H- and ¹⁹F-NMR studies support the solvent-dependent poly-pseudo-rotaxane formation at a lower concentration of L.