Three different roles of the EMIm-Es ionic liquids. In (a) and (b), EMIm-Es serves as both solvent and cationic structure-directing agents, leading to 4-connected homochiral ALF-1 with the diamond-type net (shown here is the 6-membered ring.) and 3-connected homochiral ALF-4 with the ThSi-type net (shown here is the 10-membered ring.). In (c), EMIm-Es serves only as the solvent and tetrapropylammonium cations serve as the cationic structure directing agent, leading to the formation of homochiral ALF-2 with the diamond-type net (shown here is the 6- membered ring.). In (d), both cations and anions of EMIm-Es are trapped in the cavity of 4-connected framework with the CdSO4-type topology.