Three-Dimensional Metal-Organic Frameworks Based on Functionalized Tetracarboxylate Linkers: Synthesis, Strucures, and Gas Sorption Studies

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Abstract
New tetracarboxylate ligands with dihydroxy (L1) and crown ether functionalities (L2) have been synthesized and treated with CuII and ZnII ions to generate three-dimensional (3D) metal-organic frameworks (MOFs) with the compositions of [Cu2(L1)(H2O)2]·14DMF·10H2O, 5, [Cu2(L2)(H2O)2]·12DMF, 6, [Zn6(μ4-O)(L1)2(L1-H2)]·35DMF·27H2O, 7, and [Zn3Na2(L2)2(DMF)2]·7DMF·14H2O, 8. The four compounds show different framework structures with different connectivities. Compound 5 exhibits the PtS topology whereas compound 6 has a [64.82]3[66] topology. Compound 7 adopts a new [4.65][42.68][44.62][45.6][48.610.83] topology while compound 8 exhibits the Flu topology. The porosity and H2 uptake were studied by gas sorption experiments and grand canonical Monte Carlo (GCMC) simulations. Compound 5 shows a high H2 uptake of up to 1.11 wt % at 77 K.

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