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Updated: Jan 24, 2026

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Expanding the Variety of Zirconium-based Inorganic Building Units for Metal-Organic Frameworks
Sebastian Leubner1, Haishuang Zhao2, Niels Van Velthoven3
1Institute for Inorganic Chemistry, University of Kiel, Max-Eyth Strasse 2, 24118, Kiel, Germany.
Abstract:
Two new zirconium-based metal-organic frameworks with the composition [Zr6 O4 (OH)4 (OAc)6 (BDC)3 ] (CAU-26) and [Zr5 O4 (OH)4 (OAc)4 (BDC)2 ] (CAU-27) are reported, which were synthesized from acetic acid, a rarely utilized but green and sustainable solvent (BDC2- : 1,4-benzenedicarboxylate). Structure determination aided by automated electron diffraction tomography revealed that CAU-26 is composed of layers of well-known {Zr6 O8 } clusters interconnected by terephthalate ions. In contrast CAU-27 exhibits a three-dimensional structure with a so far unknown type of one-dimensional inorganic building unit (IBU), which can be rationalized as condensed polyhedron-sharing chains of {Zr6 O8 } clusters. CAU-26 occurs as an intermediate of the CAU-27 synthesis and can be isolated easily, when reaction temperature and time are decreased. We were also able to synthesize two isoreticular derivatives of CAU-27 with extended linker molecules by implementing 4,4'-biphenyldicarboxylic acid (H2 BPDC) and 5,5'-dicarboxy-2,2'-bipyridine (H2 BIPY). All materials show high thermal and chemical stability as well as permanent microporosity. The excellent stability of CAU-27-BIPY was exploited to synthesize a performant iridium-supported heterogeneous MOF-based catalyst for the direct C-H borylation of arenes.
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