A {Ni12}-Wheel-Based Metal-Organic Framework for Coordinative Binding of Sulphur Dioxide and Nitrogen Dioxide.

Air pollutions by SO 2 and NO 2 have caused significant risks on the environment and human health. Understanding the mechanism of active sites within capture materials is of fundamental importance to the development of new clean-up technologies. Here we report the crystallographic observation of reversible coordinative binding of SO 2 and NO 2 on open Ni(II) sites in a metal-organic framework (NKU-100) incorporating an unprecedented {Ni 12 }-wheel, which exhibits six open Ni(II) sites on desolvation. Immobilised gas molecules are further stabilised by cooperative host-guest interactions comprised of hydrogen bonds, π ··· π interactions and dipole interactions. At 298 K and 1.0 bar, NKU-100 shows adsorption uptakes of 6.21 and 5.80 mmol g -1 for SO 2 and NO 2 , respectively. Dynamic breakthrough experiments have confirmed the selective retention of SO 2 and NO 2 at low concentrations under dry conditions. This work will inspire the future design of efficient sorbents for the capture of SO 2 and NO 2 .