Three-Dimensional Porous Metal–Metalloporphyrin Framework Consisting of Nanoscopic Polyhedral Cages

An unprecedented nanoscopic polyhedral cage-containing metal–metalloporphyrin framework, MMPF-1, has been constructed from a custom-designed porphyrin ligand, 5,15-bis(3,5-dicarboxyphenyl)porphine, that links Cu2(carboxylate)4 moieties. A high density of 16 open copper sites confined within a nanoscopic polyhedral cage has been achieved, and the packing of the porphyrin cages via an “ABAB” pattern affords MMPF-1 ultramicropores which render it selective toward adsorption of H2 and O2 over N2, and CO2 over CH4.