Ionothermal synthesis of a new cobalt metal-organic framework based on tetranuclear cobalt clusters

A new metal-organic network (EMIM)Co₂(hip)₂(μ₃-OH)]·H₂O (1), (H₂hip = 5-hydroxyisophthalic acid and EMIM = 1-ethly-3-methylimidazolium), has been synthesized by the ionothermal reaction of cobalt nitrate, H₂hip and EMIM]Br ionic liquid. Single-crystal X-ray diffraction analysis reveals that 1 exhibits a two-dimensional (2D) bilayer constructed from tetranuclear Co₄(μ₃-OH)₂] building units and hip²⁻ linkers. There are square cavities with the dimension of 10.161 × 10.868 Å. The EMIM]⁺ cations are located in the cavities, which have the hydrogen bonding interactions with the bilayer. Further more, the strong hydrogen bonds between the carboxylate and hydroxyl oxygen atoms of hip²⁻ ligands and lattice water molecules extend the 2D layer into a 3D supramolecular network. The magnetic properties of 1 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that there exist antiferromagnetic interactions.