New Coordination Polymers and Porous Supramolecular Metal Organic Network Based on the Trinuclear Triangular Secondary Building Unit [Cu3(μ3‑OH)(μ-pz)3]2+ and 4,4′-Bypiridine. 1°

The trinuclear triangular CuII complex [Cu3(μ3-OH)­(μ-pz)3(HCOO)2(Hpz)2] (Hpz = pyrazole) reacts with 4,4′-bipyridine (bpy) yielding a two-dimensional (2D) waved sheets, two three-dimensional (3D) coordination polymers (CPs), as well as a hexanuclear CuII cluster, depending on the reagent ratios and reaction conditions. Single crystal X-ray diffraction (XRD) determinations point out that, while CPs crystal structures are not porous, the hexanuclear CuII clusters are packed in the solid state generating a stable porous 3D supramolecular network, where two kinds of perpendicular, hydrophobic channels (ca. 4.83 × 5.86 Å2 and 4.99 × 4.79 Å2, corresponding to the 24.7% of the total crystal volume) are present. In the “as-synthesized” compound, channels of one kind are empty, while the other ones are occupied by guest bpy molecules which can be removed by soaking the crystals in suitable solvents (benzene, toluene, c-hexane) maintaining intact the crystal skeleton. Moreover, two of the above complexes act as catalysts (or catalyst precursors) in the peroxidative oxidation of cyclohexane.