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      Metal-Organic Framework (MOF) Defects under Control: Insights into the Missing Linker Sites and Their Implication in the Reactivity of Zirconium-Based Frameworks.

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          Abstract

          For three-dimensional (3D) metal-organic frameworks (MOFs), the presence and nature of structural defects has been recognized as a key factor shaping the material's physical and chemical behavior. In this work, the formation of the "missing linker" defects has been addressed in the model biphenyl-4,4'-dicarboxylate (bpdc)-based Zr MOF, UiO-67. The defect showed strong dependence on the nature of the modulator acid used in the MOF synthesis; the defects, in turn, were found to correlate with the MOF physical and chemical properties. The dynamic nature of the Zr6 (node)-monocarboxylate bond showed promise in defect functionalization and "healing", including the formation of X-ray-quality "defect-free" UiO-67 single crystals. Chemical transformations at defect sites have also been explored. The study was also extended to the isoreticular UiO-66 and UiO-68' systems.

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          Author and article information

          Journal
          Inorg Chem
          Inorganic chemistry
          1520-510X
          0020-1669
          Sep 8 2015
          : 54
          : 17
          Affiliations
          [1 ] Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007, Tarragona, Spain.
          Article
          10.1021/acs.inorgchem.5b01053
          26291237
          694d2108-80af-4d64-adea-f0cf07c4bb09

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