Lanthanide Metal–Organic Frameworks Exhibiting Fluoro-Bridged Extended Chains: Synthesis, Crystal Structures, and Magnetic Properties

Two fluoro-bridged lanthanide-containing metal–organic frameworks (MOFs) were synthesized using 2,2′-bipyridine-4,4′-dicarboxylic acid (BPDC), a fluorinated modulator, and a lanthanide nitrate. The syntheses of MOFs containing Gd3+ or Tb3+ and a closely related MOF structure containing Ho3+, Gd3+, or Tb3+ are presented. The presence of the fluorinated metal chains in these MOFs is shown through single crystal X-ray diffraction, energy dispersion X-ray spectroscopy, 19F nuclear magnetic resonance, and X-ray photoelectron spectroscopy. Magnetic measurements reveal weak antiferromagnetic exchange between the Ln3+ ions mediated by fluoride anions along the zigzag ladder chains present in the crystal structures of these MOFs.