Magnetostructural Correlations in CuII−NC−WV Linkage: The Case of [CuII(diimine)]2+−[WV(CN)8]3− 0D

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• 作者：Tomasz Korzeniak*^&#8224 ; ; Cdric Desplanches^‡ ; ; Robert Podgajny^&#8224 ; ; Carlos Gimnez-Saiz^§ ; ; Katarzyna Stadnicka^&#8224 ; ; Michał ; Ram
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：April 6, 2009
• 年：2009
• 卷：48
• 期：7
• 页码：2865-2872
• 全文大小：266K
• 年卷期：v.48,no.7(April 6, 2009)
• ISSN：1520-510X

文摘

We report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [Cu^II(phen)₃]₂{[Cu^II(phen)₂]₂[W^V(CN)₈]₂}(ClO₄)₂·10H₂O (phen = 1,10-phenanthroline) (1) and {[Cu^II(bpy)₂]₂[W^V(CN)₈]} {[Cu^II(bpy)₂][W^V(CN)₈]}·4H₂O (bpy = 2,2′-bipyridyl) (2). Compound 1 consists of cyano-bridged [Cu^II₂W^V₂]²⁻ molecular rectangles and isolated [Cu^II(phen)₃]²⁺ complexes. The molecular structure of 2 reveals cyano-bridged trinuclear [Cu^II₂W^V]⁺ and dinuclear [Cu^IIW^V]⁻ ions. Magnetic interactions in 1 are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic Cu^II−NC−W^V units (J₁ = +39(4) cm⁻¹) interacting antiferromagnetically (J₂ = −1.6(4) cm⁻¹). The analysis of the magnetic response of 2 reveals ferromagnetic interaction within the [Cu^II−NC−W^V−CN−Cu^II]⁺ and [Cu^II−NC−W^V]⁻ isolated units, characterized by J = +35(7) cm⁻¹ and antiferromagnetic coupling between them (4J′ = −0.30(8) cm⁻¹). The discussion of the magnetic behavior and the correlation of the J_CuW parameters with the geometry of cyano bridges at copper(II) centers of 1 and 2 is based on the DFT calculations, which yield J_av = +13.2 cm⁻¹ for 1 and J = +31 cm⁻¹ for 2. The domination of the ferromagnetic Cu^II−NC−W^V interaction in 1 and 2 originates from the mutual orthogonality of natural magnetic orbitals in the case of coordination of cyano bridges at the equatorial sites of Cu(II) moieties.