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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• 作者：Tamyris T. da Cunha ; Willian X. C. Oliveira ; Carlos B. Pinheiro ; Emerson F. Pedroso ; Wallace C. Nunes ; Cynthia L. M. Pereira
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：February 3, 2016
• 年：2016
• 卷：16
• 期：2
• 页码：900-907
• 全文大小：555K
• ISSN：1528-7505

文摘

Three new coordination compounds of formula (edap)b>2b>[Cu(opba)]b>2b>·4Hb>2b>O (<b>1b>), (edap)[{Nab>2b>(Hb>2b>O)b>4b>}{Cub>2b>(opba)b>2b>}]·2Hb>2b>O (<b>2b>), and (edap)[{Kb>2b>(Hb>2b>O)b>2b>}{Cub>2b>(opba)b>2b>}]·3Hb>2b>O (<b>3b>) (edap = 1,1′-ethylenebis(4-aminopyridinium) and opba = 1,2-phenylenebis(oxamate)) were synthesized through the metathesis reaction involving Ab>2b>[Cu(opba)] (A = Li⁺, Na⁺, and K⁺) and (edap)Clb>2b>·2Hb>2b>O. Crystal structures of <b>1b>–<b>3b> and edap(IOb>3b>)b>2b>·4Hb>2b>O compound were elucidated by single crystal X-ray diffraction. Compounds <b>1b>–<b>3b> are built up from dinuclear copper(II) entities, {[Cu(opba)]b>2b>}^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 (<b>1b>), 1 (<b>2b>), and 2 (<b>3b>)) in the solid state depending on the nature of the coordinated alkaline ion present alongside edap²⁺ counterions. While the {[Cu(opba)]b>2b>}^4– building blocks are well-isolated in <b>1b>, they form either double chains or corrugated layers due to the coordination of the Na⁺ or K⁺ ions in <b>2b> and <b>3b>, respectively. Magnetic properties of <b>1b>–<b>3b> show a very weak antiferromagnetic coupling between the Cu^II ions through a double monatomic (μ-O) bridge (?J = 1.63(9) (<b>1b>), 2.29(2) (<b>2b>), and 1.65(3) cm^–1 (<b>3b>)), the Hamiltonian being defined as <b>Hb> = ?(<b>Sb>b><b>1b>b>·<b>Sb>b><b>2b>b>) + g βH(<b>Sb>b><b>1b>b> + <b>Sb>b><b>2b>b>).