Synthesis, Structural Characterization, and Catalytic Performance of a Vanadium‐Based Metal–Organic Framework (COMOC‐3)

A vanadium 2,6‐naphthalenedicarboxylate, VIII(OH)(O2C–C10H6–CO2)·H2O, denoted as COMOC‐3as (COMOC = Center for Ordered Materials, Organometallics and Catalysis, Ghent University), has been synthesized under hydrothermal conditions by means of both a solvothermal and a microwave synthesis procedure. The structure shows the topology of an aluminium 2,6‐naphthalenedicarboxylate, the so‐called MIL‐69 (MIL = Materials of the Institute Lavoisier). After calcination at 250 °C in air, the VIII center was oxidized to VIV with the structure of VIVO(O2C–C10H6–CO2) (COMOC‐3). The oxidation process was verified by cyclic voltammetry and EPR spectroscopy. The crystallinity was investigated by variable‐temperature XRD. The title compound is stable against air and moisture. The catalytic performance of COMOC‐3 was examined in the liquid‐phase oxidation of cyclohexene. COMOC‐3 exhibited similar catalytic performance to MIL‐47 [VO(O2C–C6H4–CO2)]. The compound is reusable and maintains its catalytic activity through several runs.