Toluene-assisted synthesis of RHO-type zeolitic imidazolate frameworks: synthesis and formation mechanism of ZIF-11 and ZIF-12

Toluene was discovered as the structure template for the synthesis of large-cage RHO-type zeolitic imidazolate frameworks (ZIF-11 and ZIF-12) in an alcohol-based solution where benzimidazole-toluene interactions play a decisive structure-directing role; otherwise it leads to small-cage SOD-type ZIF-7 and ZIF-9 without toluene. The specific π-π interactions make toluene molecules adopt a specific and oriented arrangement in the unit cell. XRD intensity of the (100) plane is strongly dependent on the amount of toluene: apparent intensity degradation is observed after removing toluene by solvent exchange or thermal treatment, and the peak intensity is recoverable by filling of the pores with toluene vapor. More-polar methanol as compared to ethanol is favorable for the formation of RHO-type ZIFs due to the enhanced interactions between toluene and imidazolate linkers.