Host-Guest [2+2] Cycloaddition Reaction: Postsynthetic Modulation of CO2 Selectivity and Magnetic Properties in a Bimodal Metal-Organic Framework.

Simultaneous tuning of permanent porosity and modulation of magnetic properties by postsynthetic modification (PSM) with light in a metal-organic framework is unprecedented. With the aim of achieving such a photoresponsive porous magnetic material, a 3D photoresponsive biporous framework, MOF1, which has 2D channels occupied by the guest 1,2-bis(4-pyridyl)ethylene (bpee), H2 O, and EtOH molecules, has been synthesized. The guest bpee in 1 is aligned parallel to pillared bpee with a distance of 3.9 A between the ethylenic groups; this allows photoinduced PSM of the pore surface through a [2+2] cycloaddition reaction to yield MOF2. Such photoinduced PSM of the framework structure introduces enhanced CO2 selectivity over that of N2 . The higher selectivity in MOF2 than that of MOF1 is studied through theoretical calculations. Moreover, MOF2 unveils reversible changes in Tc with response to dehydration-rehydration. This result demonstrates that photoinduced PSM is a powerful tool for fabricating novel functional materials.