Synthesis and Gas Sorption Properties of Cupric Microporous Metal-Organic Framework Based on 1,1′-Ethynebenzene-3,3′,5,5′-tetracarboxylate

The synthesis, crystal structure, and sorption properties of [Cu-2(EBTC)(H2O)(2)]center dot 8H(2)O center dot DMF center dot DMSO (abbreviated as 1, EBTC=1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate; DMF=N,N-dimethyl formamide; DMSO=dimethyl sulfoxide) are reported. 1 features two kinds of cavities with a diameter of 0.85 nm and 0.85x2.15 nm, which are enclosed respectively by six and twelve tetracarboxylate-bridged [Cu-2(CO2)(4)] paddle-wheels and extended by the EBTC linkers into a three-dimensional (3D) supramolecular structure with ID channels accommodating the solvent molecules. It adopts the (3,4)-c net of fof (sqc 1575) topology, possesses very large solvent accessible pore volume which reaches 72.8% of the unit cell volume. After removal of the solvent molecules, the desolvated la exhibits permanent porosity verified by an N-2 sorption isotherm with a Langmuir surface area of 2844 m(2).g(-1) and Brunauer-Emmett-Teller (BET) surface area of 1 852 m(2).g(-1). It displays significant uptake of gases (H-2, CO2, CH4, C2H2) and relatively high adsorption enthalpies. Especially, it is notable that la exhibits the highest acetylene storage of 252 cm(3).g(-1) at 273 K under 1.0x10(5) Pa with higher adsorption enthalpy (34.5 kJ.mol(-1) at the coverage of 1 mmol.g(-1)) among all porous metal-organic materials reported to date. CCDC: 744108.