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 center dot center dot center dot 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 ZnIm(2) (namely xMeMeCH(2)@RHO-Zn(16)Im(32)) is available in multigram amounts, highly porous, and thermally stable.