Using bulky amides as the structure directing agents (SDAs) is an alternative synthetic strategy for the exploration of crystalline large pore (>= 12-membered ring) zeolitic imidazolate frameworks (ZIFs). Specifically, by using the bulky amides, dibutylformamide (DBF) and dipropylformamide (DPF) as solvent and imidazole (Im) as a ligand, two ZIFs mimicking the CAN and ALPO-5 (AFT) zeotypes with 12-membered ring (MR) pore openings were synthesized, and denoted as CAN[Zn(Im)(2)] and AFI-[Zn(Im)(2)], respectively. These two materials are the first known examples of Zn(Im)(2) polymorphs with 12-MR pores and AFI-[Zn(Im)(2)] has the largest pore apertures reported to date for ZIF materials. The concept that the bulky amides used were not simply acting as the solvent, but were in fact acting as SDAs or templates during the synthesis of the large pore ZIFs, was suggested by the closeness of the geometrical fit between the guest DBF and the can cages (composite building units) of the CAN-[Zn(Im)(2)].