Long-Range Magnetic Coupling through Extended -Conjugated Aromatic Bridges in Dinuclear Copper(II) Metallacyclophanes

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• 作者：Emilio Pardo ; Juan Faus ; Miguel Julve ; Francesc Lloret ; M. Carmen Muñ ; oz ; Joan Cano ; Xavier Ottenwaelder ; Yves Journaux ; Rosa Carrasco ; Gonzalo Blay ; Isabel Fern&aacute ; ndez ; and Rafael Ruiz-Gar
• 刊名：Journal of the American Chemical Society
• 出版年：2003
• 出版时间：September 10, 2003
• 年：2003
• 卷：125
• 期：36
• 页码：10770 - 10771
• 全文大小：123K
• 年卷期：v.125,no.36(September 10, 2003)
• ISSN：1520-5126

文摘

Self-assembly of 1,4-phenylenebis(oxamate) and 4,4'-biphenylenebis(oxamate) ligands and Cu²⁺ ions gives two new dinuclear copper(II) metallacyclophanes where the two metal centers are connected by double para-substituted aromatic diamide bridges. Despite the relatively large intramolecular Cu-Cu distance of ca. 8 and 12 Å for each complex, magnetic susceptibility measurements evidence strong to moderately strong intramolecular antiferromagnetic couplings (-J values of the order of 100 and 10 cm^-1, respectively). Density functional theory calculations on these compounds and their homologues with linear oligo-p-phenylenediamide bridges predict a rather slow exponential decay of magnetic coupling with increasing intermetal distance (r values up to 25 Å) along this novel series of dicopper metalla-amidocyclophanes.