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The macrocyclic cavitand MeMeCH  2 is used as a template for the mechanochemical synthesis of 0.2 MeMeCH  2 @RHO-Zn 16 ( Cl  2  Im ) 32 (0.2 MeMeCH  2 @ZIF-71) and RHO-Zn BIm  2 (ZIF-11) zeolitic imidazolate frameworks (ZIFs). It is shown that MeMeCH  2 significantly accelerates the mechanochemical synthesis, providing high porosity products (BET surface areas of 1140 m 2 /g and 869 m 2 /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 MeMeCH  2 -namely MeHCH  2 , Me   i   BuCH  2 , HPhCH  2 , MePhCH  2 , BrPhCH  2 , BrC5CH  2 -can serve as effective templates for the synthesis of x (cavitand)@RHO-ZnIm 2 products. The limitations on cavitand size and shape are explored in terms of their effectiveness as templates.

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