Journal
DALTON TRANSACTIONS
Volume 43, Issue 44, Pages 16846-16856Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4dt01880j
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Funding
- Ministry of Science, Research and Art Baden-Wurttemberg
- German Research Foundation (DFG) [SPP 1362]
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The syntheses and crystal structures of H-2-1,3-bdpb.MeOH, [Cu-2(II)(1,3-bdpb)(OCH3)(2)] (CFA-5) and [(CuCl)-Cl-I-(H-2-1,3-bdpb)] (H-2-1,3-bdpb = 1,3-bis(3,5-dimethyl-1H-pyrazol-4-yl)benzene) are described. The copper(II) containing metal-organic framework (termed Coordination Framework Augsburg University-5, CFA-5) crystallizes in the trigonal crystal system, within the space group R (3) over bar (no. 148) and the unit cell parameters are as follows: a = 26.839(3), c = 15.8317(16) angstrom, V = 9876.2(19) angstrom(3). CFA-5 features a two-fold interpenetrated 3-D microporous framework structure of cross-linked wheel-shaped {Cu-II(pz)(OMe)}(12) fundamental building units, each containing twelve copper(II) ions, mu(2)-bridging MeO- groups and pyrazolate (pz(-)) ligands. Replacing copper(II) acetate by copper(II) chloride in the synthesis leads to compound [(CuCl)-Cl-I(H-2-1,3-bdpb)], which crystallizes in the orthorhombic crystal system, within the space group Pnma (no. 62) and the unit cell parameters are as follows: a = 6.1784(8), b = 6.1784(8), c = 6.1784(8) angstrom, V = 1583.8(4) angstrom(3). In contrast to the former compound, CuCl(H-2-1,3-bdpb) is a non-porous compound consisting of Cu-I-Cl zigzag chains expanding in the direction [100] and H-2-1,3-bdpb ligands. CFA-5 is characterized by elemental and thermogravimetric analyses, variable temperature powder X-ray diffraction and IR-spectroscopy; and its porosity and magnetic properties are described in detail. CFA-5 shows a promising catalytic activity in the heterogeneously catalyzed aerobic oxidation of tetralin, which is compared with other catalytically active metal-organic frameworks.
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