A series of mono-, tri-, hexanuclear compounds, and coordination polymers were obtained from the reaction of [Cu3(μ3-OH)(μ-pz)3(MeCOO)2(Hpz)], 1, (Hpz = pyrazole) with H2SO4, H3PO4, HClO4, HNO3, CF3COOH, and CF3SO3H. The trinuclear [Cu3(μ3-OH)(μ-pz)3(SO4)(Hpz)3] 3H2O, 2t, forms a one-dimensional coordination polymer through bridging SO42-. The mononuclear [Cu(H2PO4)2(Hpz)4], 3m, is instead the unique (pure) compound isolated in our conditions from the reaction of 1 with H3PO4, whereas both [Cu(ClO4)2(Hpz)4], 4m, and [{Cu3(μ3-OH)(μ-pz)3(ClO4)(Hpz)3}2(μ2-ClO4)2], 4h, have been isolated from the reaction with aqueousHClO4, the latter being a hexanuclear species formed by two trinuclear triangular units connected through two bridging perchlorates. Moreover, the three already reported species [Cu3(μ3-OH)(μ-pz)3(NO3)(μ3-NO3)(Hpz)2], 5t, [{Cu3(μ3-OH)-(μ-pz)3(NO3)(Hpz)3}2(μ2-NO3)2], 5h, and [Cu(NO3)2(Hpz)4], 5m, are formed in the reaction of 1 with HNO3. Three pure fractions, containing crystals of the trinuclear [Cu3(μ3-OH)(μ-pz)3(CF3COO)2(Hpz)2], 6t, and two mononuclear adducts, [Cu(CF3COO)2(HPz)4], 6m(a), and [Cu(CF3COO)2(Hpz)2], 6m(b), have been isolated when 1 was reacted with aqueousCF3COOH.Analogously, in the reaction of 1 with CF3SO3H, three different species were obtained, the mononuclear [Cu(CF3SO3H)2(Hpz)4], 7m, the trinuclear [Cu3(μ3-OH)(μ-pz)3(CF3SO3)2(Hpz)3] 3H2O, 7t, and the hexanuclear [{Cu3(μ3-OH)(μ-pz)3(Hpz)3}{Cu3(μ3-O)(μ-pz)3(Hpz)3}](CF3SO3)3, 7h, where the two trinuclear units are strongly bonded through an unequally shared H-bond involving (μ3-OH) and (μ3-O) [O3 3 3O 2.54(1) A ° , O(2)-H(2) 3 3 3 O(1) 180]. All compounds were fully characterized by single-crystal X-ray diffraction determinations, UV-vis and IR spectra, electrospray ionization mass spectrometry, and magnetic susceptibility measurements.

Reactions of a Coordination Polymer Based on the Triangular Cluster [Cu-3(mu(3)-OH)(mu-pz)(3)](2+) with Strong Acids. Crystal Structure and Supramolecular Assemblies of New Mono-, Tri-, and Hexanuclear Complexes and Coordination Polymers

GARAU, FEDERICA;PANDOLFO, LUCIANO;
2010

Abstract

A series of mono-, tri-, hexanuclear compounds, and coordination polymers were obtained from the reaction of [Cu3(μ3-OH)(μ-pz)3(MeCOO)2(Hpz)], 1, (Hpz = pyrazole) with H2SO4, H3PO4, HClO4, HNO3, CF3COOH, and CF3SO3H. The trinuclear [Cu3(μ3-OH)(μ-pz)3(SO4)(Hpz)3] 3H2O, 2t, forms a one-dimensional coordination polymer through bridging SO42-. The mononuclear [Cu(H2PO4)2(Hpz)4], 3m, is instead the unique (pure) compound isolated in our conditions from the reaction of 1 with H3PO4, whereas both [Cu(ClO4)2(Hpz)4], 4m, and [{Cu3(μ3-OH)(μ-pz)3(ClO4)(Hpz)3}2(μ2-ClO4)2], 4h, have been isolated from the reaction with aqueousHClO4, the latter being a hexanuclear species formed by two trinuclear triangular units connected through two bridging perchlorates. Moreover, the three already reported species [Cu3(μ3-OH)(μ-pz)3(NO3)(μ3-NO3)(Hpz)2], 5t, [{Cu3(μ3-OH)-(μ-pz)3(NO3)(Hpz)3}2(μ2-NO3)2], 5h, and [Cu(NO3)2(Hpz)4], 5m, are formed in the reaction of 1 with HNO3. Three pure fractions, containing crystals of the trinuclear [Cu3(μ3-OH)(μ-pz)3(CF3COO)2(Hpz)2], 6t, and two mononuclear adducts, [Cu(CF3COO)2(HPz)4], 6m(a), and [Cu(CF3COO)2(Hpz)2], 6m(b), have been isolated when 1 was reacted with aqueousCF3COOH.Analogously, in the reaction of 1 with CF3SO3H, three different species were obtained, the mononuclear [Cu(CF3SO3H)2(Hpz)4], 7m, the trinuclear [Cu3(μ3-OH)(μ-pz)3(CF3SO3)2(Hpz)3] 3H2O, 7t, and the hexanuclear [{Cu3(μ3-OH)(μ-pz)3(Hpz)3}{Cu3(μ3-O)(μ-pz)3(Hpz)3}](CF3SO3)3, 7h, where the two trinuclear units are strongly bonded through an unequally shared H-bond involving (μ3-OH) and (μ3-O) [O3 3 3O 2.54(1) A ° , O(2)-H(2) 3 3 3 O(1) 180]. All compounds were fully characterized by single-crystal X-ray diffraction determinations, UV-vis and IR spectra, electrospray ionization mass spectrometry, and magnetic susceptibility measurements.
2010
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/2426713
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