Exploring the Scope of Macrocyclic "Shoe-last" Templates in the Mechanochemical Synthesis of RHO Topology Zeolitic Imidazolate Frameworks (ZIFs).

The macrocyclic cavitand is used as a template for the mechanochemical synthesis of 0.2@RHO-Zn() (0.2@ZIF-71) and RHO-Zn (ZIF-11) zeolitic imidazolate frameworks (ZIFs). It is shown that significantly accelerates the mechanochemical synthesis, providing high porosity products (BET surface areas of 1140 m/g and 869 m/g, respectively). Templation of RHO-topology ZIF frameworks constructed of linkers larger than benzimidazole (HBIm) was unsuccessful. It is also shown that cavitands other than -namely , , , , , -can serve as effective templates for the synthesis of (cavitand)@RHO-ZnIm products. The limitations on cavitand size and shape are explored in terms of their effectiveness as templates.