title: A Versatile CuIIMetal-Organic Framework Exhibiting High Gas Storage Capacity with Selectivity for CO2: Conversion of CO2to Cyclic Carbonate and Other Catalytic Abilities.
abstract: A linear tetracarboxylic acid ligand, H4L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) LM(M=ZnII, CuII). Framework LCucan also be obtained from LZnby post- synthetic metathesis without losing crystallinity. Compared with LZn, the LCuframework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, LCu'. At 77 K, LCu' absorbs 2.57 wt % of H2at 1 bar, which increases significantly to 4.67 wt % at 36 bar. The framework absorbs substantially high amounts of methane (238.38 cm3g-1, 17.03 wt %) at 303 K and 60 bar. The CH4absorption at 303 K gives a total volumetric capacity of 166 cm3(STP) cm-3at 35 bar (223.25 cm3g-1, 15.95 wt %). Interestingly, the NH2groups in the linker, which decorate the channel surface, allow a remarkable 39.0 wt % of CO2to be absorbed at 1 bar and 273 K, which comes within the dominion of the most famous MOFs for CO2absorption. Also, LCu' shows pronounced selectivity for CO2absorption over CH4, N2, and H2at 273 K. The absorbed CO2can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20 bar, 120 °C). Finally, LCu' is found to be an excellent heterogeneous catalyst in regioselective 1,3-dipolar cycloaddition reactions ("click" reactions) and provides an efficient, economic route for the one-pot synthesis of structurally divergent propargylamines through three-component coupling of alkynes, amines, and aldehydes.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India.
authors.forename: Dinesh
authors.initials: D
authors.lastname: De
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India.
authors.forename: Tapan K
authors.initials: TK
authors.lastname: Pal
authors.affiliation: Inorganic Materials and Catalysis Division, Central Salt and Marine Chemicals Research Institute (CSIR), Bhavnagar, 364002, Gujarat, India.
authors.forename: Subhadip
authors.initials: S
authors.lastname: Neogi
authors.affiliation: Inorganic Materials and Catalysis Division, Central Salt and Marine Chemicals Research Institute (CSIR), Bhavnagar, 364002, Gujarat, India.
authors.forename: S
authors.initials: S
authors.lastname: Senthilkumar
authors.affiliation: CReST Chemical Engineering Division, CSIR-National Chemical Laboratory, Pune, 411008, India.
authors.forename: Debasree
authors.initials: D
authors.lastname: Das
authors.affiliation: CReST Chemical Engineering Division, CSIR-National Chemical Laboratory, Pune, 411008, India.
authors.forename: Sayam Sen
authors.initials: SS
authors.lastname: Gupta
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India. pkb@iitk.ac.in.
authors.forename: Parimal K
authors.initials: PK
authors.lastname: Bharadwaj
keywords: CO2 absorption; click reactions; cyclic carbonate; heterogeneous catalysis; metal-organic frameworks