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• W1983251115 endingPage "256" @default.
• W1983251115 startingPage "249" @default.
• W1983251115 abstract "The isomorphous coordination polymers {micro-Au(CN)(2)](2)[(M(NH(3))(2))(2)(mu-bpym)]}[Au(CN)(2)](2) (M = Co(II) (1), Ni(II) (2), Cu(II) (3)) have been prepared from the reaction of 2 equiv. M(NO(3))(2) x nH(2)O (M = Cu(II), n = 3; M = Ni(II) and Co(II), n = 6) with 1 equiv. of bipyrimidine (bpym) in aqueous ammonia and then with an aqueous solution containing 1 equiv. of K[Au(CN)(2)]. The structures of these complexes are made of bpym bridged centrosymmetric dinuclear [M(NH(3))(2)(mu-bpym)M(NH(3))(2)] units connected by [Au(CN)(2)](-) anions to four other dinuclear units giving rise to a cationic 2D (4,4) rectangular grid network, its charge being balanced by two non-coordinated [Au(CN)(2)](-). The layers are stacked in such a way that the ammonia coordinated molecules are interdigitated and aligned above and below one sheet with cavities in neighbouring sheets, giving rise to an ABAB[dot dot dot] repeat pattern of layers. Gold atoms of bridging and non-bridging dicyanoaurate anions are involved in short aurophilic interactions (Au1-Au2 distances in the range 3.12-3.14 Angstrom), leading to a chain of gold atoms running along the a direction. Neighbouring gold chains are further connected by weaker aurophilic interactions (Au1-Au1 distances in the range 3.43-3.49 Angstrom), affording a honeycomb-like 2D network of gold atoms. The (4,4) rectangular sheets and (6,3) honeycomb sheets share the Au2 atoms, leading to a unique 3D network. Magnetic measurements clearly show the existence of antiferromagnetic exchange coupling between the metal ions with susceptibility maxima at 17 K (1), 22 K (2), and 17 K (3). The data of 1 were analyzed through a full Hamiltonian involving spin-orbit coupling, axial distortion, Zeeman interactions and magnetic exchange coupling between Co(II), and the best fit gives J = -9.23 cm(-1), kappa = 0.99, lambda = -142 cm(-1), Delta = -562 cm(-1). For 2 and 3, magnetic data were fitted to the theoretical equations derived from the isotropic Hamiltonian: H = -JS(1)S(2). The best fit parameters were g = 2.050(1), J = -17.51(1) and P = 0.01(2) for 2 and g = 2.068(5), J = -20.07(8) and P = 0.015(4) for 3, respectively (P takes into account the amount of paramagnetic impurity). In order to explain the weak magnetic interaction between copper(II) ions mediated by the bipyrimidine bridging ligand in 3, we have carried out electronic structure calculations based on the density functional theory (DFT)." @default.
• W1983251115 created "2016-06-24" @default.
• W1983251115 creator A5012286685 @default.
• W1983251115 creator A5044372615 @default.
• W1983251115 creator A5077043739 @default.
• W1983251115 creator A5079780490 @default.
• W1983251115 date "2007-01-01" @default.
• W1983251115 modified "2023-09-27" @default.
• W1983251115 title "Interplay between covalent and aurophilic interactions in a series of isostructural 3D Hoffman-like frameworks containing bipyrimidine and dicyanoaurate bridges. X-Ray structure and magnetic properties of {(µ-Au(CN)₂]₂[(M(NH₃)₂)₂(µ-bpym)]}[Au(CN)₂]₂(M = Ni(<scp>ii</scp>), Co(<scp>ii</scp>) and Cu(<scp>ii</scp>))" @default.
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• W1983251115 doi "https://doi.org/10.1039/b611684a" @default.
• W1983251115 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/17180193" @default.
• W1983251115 hasPublicationYear "2007" @default.
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