Synthesis and Structural Characterizations of New Coordination Polymers Generated by the Interaction Between the Trinuclear Triangular SBU [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ and 4,4′-Bipyridine. 3°

The reactions of 4,4′-bipyridine with selected trinuclear triangular copper­(II) complexes, [Cu₃(μ₃-OH)­(μ-pz)₃(RCOO)₂L_<i>x</i>], [pz = pyrazolate anion, R = CH₃(CH₂)_<i>n</i> (2 ≤ <i>n</i> ≤ 5); L = H₂O, MeOH, EtOH] yielded a series of 1D coordination polymers (CPs) based on the repetition of [Cu₃(μ₃-OH)­(μ-pz)₃] secondary building units joined by bipyridine. The CPs were characterized by conventional analytical methods (elemental analyses, ESI-MS, IR spectra) and single crystal XRD determinations. An unprecedented 1D CP, generated through the bipyridine bridging hexanuclear copper clusters moieties, two 1D CPs presenting structural analogies, and two monodimensional tapes having almost exactly superimposable structures, were obtained. In one case, the crystal packing makes evident the presence of small, not-connected pores, accounting for ca. 6% of free cell volume

Interaction of the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ with 4,4′-Bipyridine. Structural Characterizations of New Coordination Polymers and Hexanuclear Cu^II Clusters. 2°

By reacting 4,4′-bipyridine (bpy) with selected trinuclear triangular Cu^II complexes, [Cu₃(μ₃-OH)­(μ-pz)₃­(RCOO)₂­(LL′)] [pz = pyrazolate anion; R = CH₃, CH₃CH₂, CH₂CH, CH₂C­(CH₃); L, L′ = Hpz, H₂O, MeOH] in MeOH, the substitution of monotopic ligands by ditopic bpy was observed. Depending on the stoichiometric reaction ratios, different compounds were isolated and structurally characterized. One- and two-dimensional coordination polymers (CPs), as well as two hexanuclear Cu^II clusters were identified. One of the hexanuclear clusters self-assembles into a supramolecular three-dimensional structure, and its crystal packing shows the presence of two intersecting channels, one of which is almost completely occupied by guest bpy, while in the second one guest water molecules are present. This compound also shows a reversible, thermally induced, single-crystal-to-single-crystal transition

From Thioxo Cluster to Dithio Cluster: Exploring the Chemistry of Polynuclear Zirconium Complexes with S,O and S,S Ligands

Three different zirconium thio and oxothio clusters, characterized by different coordination modes of dithioacetate and/or monothioacetate ligands, were obtained by the reaction of monothioacetic acid with zirconium <i>n</i>-butoxide, Zr(OⁿBu)₄, in different experimental conditions. In particular, we isolated the three polynuclear Zr₃(μ₃-SSSCCH₃)₂(SSCCH₃)₆·2ⁿBuOH (<b>Zr</b>_<b>3</b>), Zr₄(μ₃-O)₂(μ−η¹-SOCCH₃)₂(SOCCH₃)₈(OⁿBu)₂ (<b>Zr</b>_<b>4</b>), and Zr₆(μ₃-O)₅(μ-SOCCH₃)₂(μ-OOCCH₃)(SOCCH₃)₁₁(ⁿBuOH) (<b>Zr</b>_<b>6</b>) derivatives, presenting some peculiar characteristics. <b>Zr</b>_<b>6</b> has an unusual star-shaped structure. Only sulfur-based ligands, viz., chelating dithioacetate monoanions and an unusual ethane-1,1,1-trithiolate group μ₃ coordinating the Zr ions, were observed in the case of <b>Zr</b>_<b>3</b>. 1D and 2D NMR analyses confirmed the presence of differently coordinated ligands. Raman spectroscopy was further used to characterize the new polynuclear complexes. Time-resolved extended X-ray absorption fine structure measurements, devoted to unraveling the cluster formation mechanisms, evidenced a fast coordination of sulfur ligands and subsequent relatively rapid rearrangements

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

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 Cu^II 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 Cu^II 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 Cu^II 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 Ų and 4.99 × 4.79 Ų, 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, <i>c</i>-hexane) maintaining intact the crystal skeleton. Moreover, two of the above complexes act as catalysts (or catalyst precursors) in the peroxidative oxidation of cyclohexane

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 Cu^II 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 Cu^II 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 Cu^II 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 Ų and 4.99 × 4.79 Ų, 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, <i>c</i>-hexane) maintaining intact the crystal skeleton. Moreover, two of the above complexes act as catalysts (or catalyst precursors) in the peroxidative oxidation of cyclohexane