Paredes-García Verónica, Vega Andrés, Novak Miguel A, Vaz Maria G F, Souza Denise A, Venegas-Yazigi Diego, Spodine Evgenia
Departamento de Química, Universidad Tecnológica Metropolitana, Chile.
Inorg Chem. 2009 Jun 1;48(11):4737-42. doi: 10.1021/ic8019292.
A structural and magnetic characterization of a trinuclear chiral Mn(II) formate three-dimensional framework exhibiting a triangular arrangement is presented. Compound Na(3)[Mn(3)(HCOO)(9)] was obtained by solvothermal synthesis and crystallizes in the chiral cubic space group P2(1)3 and is well described by a Delta conformation. The structure displays triangular Mn(3) building blocks, in which the metal centers are bonded by formate ligands in a syn-anti mode (Mn-Mn 5.697(1) A). The coordination sphere of manganese(II) is completed by six oxygen atoms from six formate ligands, resulting in an octahedral geometry. Magnetic susceptibility measurements showed antiferromagnetic interactions at high temperature and a strongly field dependent magnetic behavior below 40 K. At fields higher than 1.0 kOe only the antiferromagnetic interactions can be observed. At applied fields lower than 1.0 kOe magnetic susceptibility becomes irreversible with maxima observed at 22 and 34 K. These maxima suggest a weak ferromagnetic behavior because of spin canting, allowed by the presence of the noncentrosymmetric syn-anti HCOO bridges linking the Mn sites. This non-collinear antiferromagnetism and irreversible behavior can be due to the existence of a high degree of frustration in this unique lattice composed of linked triangular arrangements of interacting magnetic centers.
本文介绍了一种具有三角形排列的三核手性甲酸锰(II)三维骨架的结构和磁性表征。化合物Na(3)[Mn(3)(HCOO)(9)]通过溶剂热合成法获得,结晶于手性立方空间群P2(1)3中,可用Δ构象很好地描述。该结构展示了三角形的Mn(3)结构单元,其中金属中心通过甲酸根配体以顺-反模式键合(Mn-Mn 5.697(1) Å)。锰(II)的配位球由六个甲酸根配体的六个氧原子完成,形成八面体几何构型。磁化率测量表明,在高温下存在反铁磁相互作用,在40 K以下存在强烈的场依赖磁性行为。在高于1.0 kOe的场中,只能观察到反铁磁相互作用。在低于1.0 kOe的外加场中,磁化率变得不可逆,在22 K和34 K处观察到最大值。这些最大值表明由于自旋倾斜而存在弱铁磁行为,这是由连接Mn位点的非中心对称顺-反HCOO桥的存在所允许的。这种非共线反铁磁性和不可逆行为可能是由于在这个由相互作用的磁性中心的连接三角形排列组成的独特晶格中存在高度的几何失配。