[Cu4OCl6(DABCO)(2)] center dot 0.5DABCO center dot 4CH(3)OH (MFU-5): Modular synthesis of a zeolite-like metal-organic framework constructed from tetrahedral {Cu4OCl6} secondary building units and linear organic linkers

A novel metal-organic framework (MOF) based on a tetranuclear copper cluster and a linear organic ligand formulated as [Cu40Cl6(DABCO)(2)]center dot 0.5DABCO center dot 4CH(3)OH (denoted as MFU-5, MFU=Metal-Organic Framework, Ulm University: DABCO = 1,4-diazabicyclo[2.2.2]octane), was prepared via solvothermal synthesis. In contrast with common MOF synthesis strategies, MFU-5 is assembled from pre-defined molecular secondary building units, i-e. {Cu40Cl6} moieties, which become the nodes of the coordination framework. The title compound was characterized by single crystal X-ray diffraction, variable temperature powder diffraction (VT-XRPD), thermal analysis, as well as IR- and UV/Vis spectroscopy. Crystal data for MFU-5: hexagonal, P6/mcc (no. 192), a=25.645(9), c=17.105(11)angstrom, V=9742(8)angstrom(3), Z=12, 1690 structure factors, R[F-2>2 sigma-(F-2)]=0.049. MFU-5 is a 3D metal-organic framework with I D channels running along the c-axis hosting DABCO and methanol solvent molecules. The framework displays a zeolite-like structure constructed from mso cages, which represents the composite building units in the zeolites SSF, MSO and SZR. Two-fold interpenetration is observed between these building units. TG/DTA-MS and VT-XRPD characterization reveal a stepwise release of methanol and DABCO molecules upon heating, eventually resulting in a structural change into a nonporous material. (C) 2009 Elsevier Inc. All rights reserved.