Higher Symmetry Multinuclear Clusters of Metal–Organic Frameworks for Highly Selective CO2 Capture

A new approach of finely tuning multinuclear clusters of metal–organic frameworks (MOFs) through symmetry-upgradingly isoreticular transformation was first presented and a bcu-type MOF, {[Cu4(μ4-O)­Cl2(IN)4]­[CuCl2]}∞ (NJU-Bai35; NJU-Bai for Nanjing University Bai group), with cluster [Cu4(μ4-O)­Cl2(COO)4N4] of higher symmetry compared to the pristine MOF, was successfully synthesized. The symmetry upgrading implemented on the inorganic part triggers the adjustment of channels in NJU-Bai35 to fit CO2 molecules, leading to a high CO2 adsorption capacity (7.20 wt % at ∼0.15 bar and 298 K) and high selectivity of CO2 over N2 and CH4 (275.8 for CO2/N2 and 11.6 for CO2/CH4) in NJU-Bai35. Breakthrough experiments further confirmed that NJU-Bai35 might be an excellent candidate for CO2 capture and natural gas purification.