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Keywords:

  • Metal-organic frameworks;
  • MOF;
  • Porous solids;
  • Cobalt;
  • Redox-active frameworks;
  • Catalysis;
  • Cyclohexene

Abstract

A metal-organic framework (MOF) containing redox active CoII atoms, [CoII(BPB)]·3DMF (1), has been prepared from the solvothermal reaction of CoII nitrate and 1,4-bis(4′-pyrazolyl)benzene (H2-BPB) in dimethylformamide (DMF). Compound 1 constitutes a porous coordination framework that is built up by interconnecting 1D CoII polymer chains with (BPB)2− ligands. The thermal stability of 1 was investigated by thermogravimetric (TG) analysis and variable-temperature X-ray powder diffraction (VTXRPD), which indicate that the framework of 1 is stable upon removal of solvent molecules. The argon adsorption isotherm of 1 at 77 K indicates a porous structure with a BET surface area of 1207 m2/g. As a test reaction for catalytic activity of 1, the oxidation of cyclohexene was examined employing tert-butyl hydroperoxide as oxidant. The maximum substrate conversion achieved after 12 h was 62 % with an estimated turn-over number (TON) of 44 based on the number of converted substrate molecules (cyclohexene) per CoII atom.