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Ga-71 Slow-CTMAS NMR and Crystal Structures of MOF-Type Gallium Carboxylates with Infinite Edge-Sharing Octahedra Chains (MIL-120 and MIL-124)

  作者 Hajjar, R; Volkringer, C; Loiseau, T; Guillou, N; Marrot, J; Ferey, G; Margiolaki, I; Fink, G; Morais, C; Taulelle, F  
  选自 期刊  CHEMISTRY OF MATERIALS;  卷期  2011年23-1;  页码  39-47  
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[摘要]Two gallium carboxylates of MOF-type have been hydrothermally synthesized (210 degrees C) by using 1,2,4,5-benzenetetracarboxylate (Ga-4(OH)(8)[C10O8H2]center dot 5-5.6H(2)O or MIL-120) or 1,2,4-benzenetri-carboxylate (Ga-2(OH)(4)[C9O6H4] or MIL-124) as linkers. The structures of both compounds solved from XRD analysis, revealed two independent crystallographic sites for the gallium atoms, which are connected to each other through mu(2)-hydroxo edge, generating zigzag chains with a cis-trans mode. The inorganic ribbons are linked to each other via all the carboxylatc functions of the pyromellitate ligand to form a 3D framework (MIL-120) or two of the carboxylate arms of the trimellitate ligand to form a 2D structure (MIL-124). For the latter, one of the carboxylate arms is not bonded to the gallium centers, resulting in the layered aspect of the final structure. Solid-state NMR using the slow-CTMAS method has been successfully implemented for the determination of the gallium site parameters for MIL-120, allowing more resolved spectra at moderate magnetic fileds than at very high field. Only one gallium site is visible for MIL-124, indicating a dynamic disorder resulting from the nonfully connected carboxylate species of the trimellitate ligand.

 
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