A Metallosupramolecular Octahedron Assembled from Twelve Copper(I) Metal Ions and Six 4,4 %26apos;-(1,2-Phenylene)bis(3,5-dimethylpyrazol-1-ide) Ligands

作者：Grzywa Maciej; Bredenkoetter Bjoern; Denysenko Dmytro; Spirkl Sebastian; Nitek Wojciech; Volkmer Dirk^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2013, 639(8-9): 1461-1471.

DOI：10.1002/zaac.201300094

• Coordination chemistry
• Metal-organic polyhedron
• Copper
• Oxygen activation

The novel coordination compound [Cu-12(I)(C16H16N4)(6)]center dot 8DMAc, (2), (DMAc = N,N-dimethylacetamide) was prepared in solvothermal or microwave assisted reaction. It contains four metallamacrocyclic trinuclear copper(I) pyrazolate coordination units, which occupy four (opposite) faces of an imaginary metallosupramolecular octahedron. Six (4,4%26apos;-(1,2-phenylene)bis(3,5-dimethylpyrazol-1-ide) ligands (L-1(2-)) are placed at the corners of the octahedron. Crystals of the free ligand H2L1 [1,2-bis(3,5-dimethyl-1H-pyrazol-4-yl)benzene, (1)], and [Cu-12(I)(C16H16N4)(6)]center dot 8DMAc (2), were characterized by single-crystal-ray structure analyses. Lingand 1 crystallizes in the monoclinic crystal system, with: a = 9.0118(9), b = 14.0075(11), c = 11.7484(11) angstrom, beta = 104.945(5), V = 1432.9(2) angstrom(3), space group P2(1)/c (no. 14). Compound 2 crystallizes in the tetragonal system, with: a = b = 19.506(5), c = 42.888(5) angstrom, V = 16318(6) angstrom(3), space group I4(1)/amd (no. 141). Compound 2 represents a porous structure, where each metallosupramolecular octahedron encloses a solvent-filled cavity of 889 angstrom(3) (accounting for 6 DMAc molecules, 21.8% of the cell volume). The incomplete crystal packing arrangement of adjacent [Cu-12(I)(C16H16N4)(6)] moieties in addition leads to solvent-filled interstitial voids accounting to 8.1% of the cell volume. Removing solvent molecules in vacuo is accompanied by reversible structural changes, leading to a partial loss of porosity, as revealed by Ar-BET sorption analysis. Compounds 1 and 2 were further characterized by elemental and thermogravimetric analysis, X-ray powder diffraction, FTIR-, UV/Vis- and fluorescence spectroscopy. Preliminary results on the activation of molecular oxygen by compound 2 are presented.

• 出版日期2013-7