title: One-dimensional and two-dimensional coordination polymers from self-assembling of trinuclear triangular Cu(II) secondary building units.
abstract: The reactions of pyrazole (Hpz) with some copper(II) carboxylates in the presence of water yield trinuclear copper derivatives characterized by the triangular core [Cu3mu3-OH)(mu-pz)3(RCOO)2] (R = H, C2H5, C3H7). Copper(II) formate gives [Cu3(mu3-OH)(mu-pz)3(HCOO)2(Hpz)2] (1), whereas copper propionate and butyrate afford [Cu3(mu3-OH)(mu-pz)3(C2H5COO)2(EtOH)] (2) and [Cu3(mu3-OH)(mu-pz)3(C3H7COO)2(MeOH)(H2O)] (3), respectively, both containing solvent molecules coordinated to copper atoms. Magnetic susceptibilities are consistent with a single unpaired electron for each trinuclear unit of 1-3, and EPR measurements indicate that higher spin states, generated by exchange coupling between copper atoms, may be populated at room temperature. Density-functional calculations provide the description of the electronic structures of 1-3, allowing, at the same time, the assignment of their UV-vis absorption spectra. X-ray molecular structure determinations show that triangular trinuclear units of 1 are connected to each other through single formate bridges, forming one-dimensional (1D) zigzag coordination polymers, whereas in 2 and 3, two oxygen atoms of two carboxylate ions doubly bridge two copper atoms of different triangles, thus generating hexanuclear units. Moreover, in 2, two other propionate ions link together two hexanuclear units yielding a 12-membered cycle and giving rise to 1D coordination polymers. The supramolecular assemblies of 1-3 are compared to that of the previously reported trinuclear triangular copper(II) derivative [Cu3(mu3-OH)(mu-pz)3(CH3COO)2(Hpz)] (A), where a two-dimensional (2D) coordination polymer is present. The reactions of 3,5-dimethylpyrazole (Hpz) with copper(II) carboxylates in the same conditions yield 1:2 Cu(RCOO)2/Hpz adducts.
authors.affiliation: Department of Chemical Sciences, University of Padova, Via Marzolo, 1, I-35131 Padova, Italy.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Casarin
authors.forename: Carlo
authors.initials: C
authors.lastname: Corvaja
authors.forename: Corrado
authors.initials: C
authors.lastname: Di Nicola
authors.forename: Daniele
authors.initials: D
authors.lastname: Falcomer
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Franco
authors.forename: Magda
authors.initials: M
authors.lastname: Monari
authors.forename: Luciano
authors.initials: L
authors.lastname: Pandolfo
authors.forename: Claudio
authors.initials: C
authors.lastname: Pettinari
authors.forename: Fabio
authors.initials: F
authors.lastname: Piccinelli
mesh_terms: D003300:Copper / Q000737:chemistry*; D003460:Crystallization; D008958:Models, Molecular; D015394:Molecular Structure; D011108:Polymers / Q000737:chemistry*; D011720:Pyrazoles / Q000737:chemistry
chemical_list: D011108:Polymers; D011720:Pyrazoles; C031280:pyrazole; D003300:Copper