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 Å 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.
Chemistry and Physics of Materials Unit (CPMU), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, Karnataka, India.
Arpan
0000-0001-7383-7416
A
Hazra
Chemistry and Physics of Materials Unit (CPMU), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, Karnataka, India.
Satyanarayana
S
Bonakala
Chemistry and Physics of Materials Unit (CPMU), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, Karnataka, India.
Karteek K
KK
Bejagam
Chemistry and Physics of Materials Unit (CPMU), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, Karnataka, India.
Sundaram
0000-0002-3355-6764
S
Balasubramanian
Chemistry and Physics of Materials Unit (CPMU), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, Karnataka, India. tmaji@jncasr.ac.in.
Tapas Kumar
0000-0002-7700-1146
TK
Maji
cycloaddition; host-guest systems; magnetic properties; metal-organic frameworks; postsynthetic modification