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Author Spotlight: A Rapid, Microwave-Assisted Hydrothermal Synthesis Of Nickel Hydroxide Nanosheets
Published on: August 18, 2023
An octa-nuclear nickel(II) pyrazolate cluster with a cubic Ni8 core and its methyl- and n-octyl-functionalized
Wisam A Al Isawi1, Matthias Zeller2, Gellert Mezei1
1Western Michigan University, Department of Chemistry, 1903 W. Michigan Ave., Kalamazoo, MI 49008, USA.
Abstract:
The mol-ecular and crystal structure of a discrete [Ni8(μ4-OH)6(μ-4-Rpz)12]2- (R = H; pz = pyrazolate anion, C3H3N2 -) cluster with an unprecedented, perfectly cubic arrangement of its eight Ni centers is reported, along with its lower-symmetry alkyl-functionalized (R = methyl and n-oct-yl) derivatives. Crystals of the latter two were obtained with two identical counter-ions (Bu4N+), whereas the crystal of the complex with the parent pyrazole ligand has one Me4N+ and one Bu4N+ counter-ion. The methyl derivative incorporates 1,2-di-chloro-ethane solvent mol-ecules in its crystal structure, whereas the other two are solvent-free. The compounds are tetra-butyl-aza-nium tetra-methyl-aza-nium hexa-μ4-hydroxido-dodeca-μ2-pyrazolato-hexa-hedro-octa-nickel, (C16H36N)(C4H12N)[Ni8(C3H3N2)12(OH)6] or (Bu4N)(Me4N)[Ni8(μ4-OH)6(μ-pz)12] (1), bis-(tetra-butyl-aza-nium) hexa-μ4-hydroxido-dodeca-μ2-(4-methyl-pyrazolato)-hexa-hedro-octa-nickel 1,2-di-chloro-ethane 7.196-solvate, (C16H36N)2[Ni8(C4H5N2)12(OH)6]·7.196C2H4Cl2 or (Bu4N)2[Ni8(μ4-OH)6(μ-4-Mepz)12]·7.196(ClCH2CH2Cl) (2), and bis-(tetra-butyl-aza-nium) hexa-μ4-hydroxido-dodeca-μ2-(4-octylpyrazolato)-hexa-hedro-octa-nickel, (C16H36N)2[Ni8(C11H19N2)12(OH)6] or (Bu4N)2[Ni8(μ4-OH)6(μ-4-Octpz)12] (3). All counter-ions are disordered (with the exception of one Bu4N+ in 3). Some of the octyl chains of 3 (the crystal is twinned by non-merohedry) are also disordered. Various structural features are discussed and contrasted with those of other known [Ni8(μ4-OH)6(μ-4-Rpz)12]2- complexes, including extended three-dimensional metal-organic frameworks. In all three structures, the Ni8 units are lined up in columns.
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