Manipulating the supramolecular assembly of γ-cyclodextrin and Anderson polyoxometalate hybrids through variations in remote functionality

Understanding and controlling the primary interactions between molecule-based building blocks is of fundamental importance to design hierarchical supramolecular assemblies at the nanoscopic scale and to create potential functionality. Herein, we present how subtle changes of the remote functional groups of Anderson-type polyoxometalate hybrids can have significant influence on their molecular interactions upon complexation with γ-cyclodextrins, giving rise to supramolecular assemblies ranging from 3D square-plate-like frameworks to 1D inclusion-and-threading polyrotaxanes. The effects of the remote functionalities upon supramolecular associations are studied in solution using 1H-nuclear magnetic resonance (NMR), 2D NOESY NMR, isothermal titration calorimetry, and electrospray ionization mass spectroscopy and in solid state by single-crystal X-ray. Achiral fluorophores are incorporated into the structures of supramolecular complexes to assemble functional materials that exhibit circularly polarized luminescence. This work provides pathways for the fine-tuning of supramolecular self-assemblies at the molecular level and the design of multifunctional materials.