Rational Design and Assembly of a New Series of Cyanide-Bridged FeIII−MnII One-Dimensional Single Chain Complexes: Synthesis, Crystal Structures, and Magnetic Properties

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• 作者：Daopeng Zhang ; Hailong Wang ; Yuting Chen ; Zhong-Hai Ni ; Laijin Tian ; Jianzhuang Jiang
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：June 15, 2009
• 年：2009
• 卷：48
• 期：12
• 页码：5488-5496
• 全文大小：992K
• 年卷期：v.48,no.12(June 15, 2009)
• ISSN：1520-510X

文摘

Two mononuclear seven-coordinated macrocycle manganese(II) compounds and three dicyanide-containing precursors have been employed as building blocks to assemble cyanide-bridged heterobimetallic complexes, resulting in five new cyanide-bridged single chain complexes {[Mn(L¹)][Fe(bpb)(CN)₂]}ClO₄·0.5H₂O (2), {[Mn(L²)][Fe(bpb)(CN)₂]}ClO₄·0.5H₂O (3), {[Mn(L¹)][Fe(bpClb)(CN)₂]}ClO₄·H₂O (4), {[Mn(L²)][Fe(bpClb)(CN)₂]}ClO₄·0.5H₂O (5), and {[Mn(L¹)][Fe(bpdBrb)(CN)₂]}ClO₄·H₂O (6). Single X-ray diffraction analysis reveals their one-dimensional (1D) single cyanide-bridged cationic polymeric chain structure consisting of alternating units of [Mn(L)]²⁺ (L = L¹ or L²) and [Fe(L′)(CN)₂]⁻ (L′ = bpb^2-, bpClb^2- or bpdBrb^2-) with free ClO₄⁻ as balanced anion. Similar to the mononuclear macrocyclic manganese(II) precursor {[Mn(L²)(H₂O)Cl]ClO₄}·CH₃OH (1), the coordination geometry of manganese(II) ion in all the 1D complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and N₅ or N₃O₂ coordinating mode at the equatorial plane from ligand L¹ or L². Investigation of the magnetic properties of these five 1D single chain cyanide-bridged Fe^III−Mn^II complexes reveals the antiferromagnetic magnetic coupling between neighboring Fe(III) and Mn(II) ions through the bridging cyanide group. A best-fit to the magnetic susceptibilities of these complexes based on the 1D alternating chain model leads to the magnetic coupling constants J₁ = −1.16(2) and J₂ = −0.10(3) cm⁻¹ for 2, J₁ = −3.10(1) and J₂ = −0.25(1) cm⁻¹ for 3, J₁ = −1.10(1) and J₂ = −0.139(8) cm⁻¹ for 4, J₁ = −1.99(6) and J₂ = −0.57(1) cm⁻¹ for 5, and J₁ = −1.23(1) and J₂ = −0.13(5) cm⁻¹ for 6, respectively. This work will provide valuable information for the rational design and synthesis of low-dimensional, in particular, single chain, cyanide-bridged magnetic complexes.