Use of a “Shoe-Last” Solid-State Template in the Mechanochemical Synthesis of High-Porosity RHO-Zinc Imidazolate

We report the first use of a nonionic solid (NIS) as a template in mechanosynthesis of a metal–organic framework. Through eight intermolecular C–H···O hydrogen bonds, the macrocyclic MeMeCH2 template predictably functions as a “shoe-last” for the assembly of double-eight rings in the liquid-assisted reaction of ZnO and imidazole (ImH). The resulting new form of ZnIm2 (namely xMeMeCH2@RHO-Zn16Im32) is available in multigram amounts, highly porous, and thermally stable.