Alkaline ion-modulated solid-state supramolecular organization in mixed organic/metallorganic compounds based on 1,1'-ethylenebis(4-aminopyridinium) cations and bis(oxamate)cuprate(ii) anions
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Universidade Federal de Minas Gerais
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Three new coordination compounds of formula (edap)2[Cu(opba)]2·4H2O (1), (edap)[{Na2(H2O)4}{Cu2(opba)2}]·2H2O (2), and (edap)[{K2(H2O)2}{Cu2(opba)2}]·3H2O (3) (edap = 1,1′-ethylenebis(4-aminopyridinium) and opba = 1,2-phenylenebis(oxamate)) were synthesized through the metathesis reaction involving A2[Cu(opba)] (A = Li+, Na+, and K+) and (edap)Cl2·2H2O. Crystal structures of 1–3 and edap(IO3)2·4H2O compound were elucidated by single crystal X-ray diffraction. Compounds 1–3 are built up from dinuclear copper(II) entities, {[Cu(opba)]2}4– with an asymmetric bis(monatomic oxygen) bridge resulting from the parallel “out-of-plane” disposition of the planar mononuclear [Cu(opba)]²–. They possess distinct supramolecular arrangements of varying dimensionality (nD with n = 0 (1), 1 (2), and 2 (3)) in the solid state depending on the nature of the coordinated alkaline ion present alongside edap²+ counterions. While the {[Cu(opba)]2}4– building blocks are well-isolated in 1, they form either double chains or corrugated layers due to the coordination of the Na+ or K+ ions in 2 and 3, respectively. Magnetic properties of 1–3 show a very weak antiferromagnetic coupling between the Cu II ions through a double monatomic (μ-O) bridge (−J = 1.63(9) (1), 2.29(2) (2), and 1.65(3) cm–¹ (3)), the Hamiltonian being defined as H = −(S1·S2) + g βH(S1 + S2).
Abstract
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Química supramolecular, Cristalografia, Cristalografia de raio X, Cristais Propriedades magnéticas, Forças intermoleculares, Compostos de coordenação, Antiferromagnetismo, Cátions, Íons
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Cations, Counterions, Crystal structure, Ions, Molecules
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https://pubs.acs.org/doi/10.1021/acs.cgd.5b01453