Syntheses, crystal structures, and magnetic properties of cyano-bridged Mn(II)-Nb(IV) bimetal assemblies

Kosuke Nakagawa; Kenta Imoto; Hiroyuki Miyahara; Shin-ichi Ohkoshi

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Syntheses, crystal structures, and magnetic properties of cyano-bridged Mn(II)-Nb(IV) bimetal assemblies

机译：氰基桥联的Mn（II）-Nb（IV）双金属组装体的合成，晶体结构和磁性

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In this paper, we report the syntheses, crystal structures, and magnetic properties of two manganese(II)- octacyanoniobate(IV)-based magnets: Mn~(II) _2[Nb~(IV)(CN)_8](3-pyridinemethanol)_8·2H_2O (1) and Mn~(II) _2[Nb~(IV) (CN)8](3-aminopyridine)8·2H_2O (2). 1 and 2 possess 3D network structures where a [Nb(CN)_8]~(4-) ion is connected to four Mn ions, and a Mn ion is connected to two [Nb(CN)8]4- ions via bridged cyanides. The coordination geometry of [Nb(CN)_8] in 1 is square antiprism, while that in 2 is dodecahedron. Magnetic measurements show that 1 and 2 are ferrimagnets with Curie temperatures (TC) of 24 and 43 K, respectively, although the coordination numbers of the bridged CN groups around Nb and Mn ions are the same. The difference in TC can be understood by considering the difference in the coordination geometries of [Nb(CN)_8]. Molecular orbital calculations of [Nb~(IV)(CN)_8] using the discrete variational (DV)-Xa method indicate that the population of the 2p orbital on the bridged N with a dodecahedron geometry is larger than that with a square antiprism geometry. The calculation results suggest that the charge population of the 2p orbital on the cyano-nitrogen affects the superexchange interaction for the magneticorbital of NbAC"NAMn, which determines the TC value.

机译：在本文中，我们报告了两种基于锰（II）-八氰基铌酸盐（IV）的磁体的合成，晶体结构和磁性能：Mn〜（II）_2 [Nb〜（IV）（CN）_8]（3-吡啶甲醇）_8·2H_2O（1）和Mn〜（II）_2 [Nb〜（IV）（CN）8]（3-氨基吡啶）8·2H_2O（2）。图1和图2具有3D网络结构，其中[Nb（CN）_8]〜（4-）离子连接至四个Mn离子，并且Mn离子通过桥连氰化物连接至两个[Nb（CN）8] 4-离子。 [Nb（CN）_8]在1中的配位几何是方形反棱镜，而在2中是十二面体。磁测量表明1和2是居里温度（TC）为24 K和43 K的亚铁酸盐，尽管在Nb和Mn离子周围的桥连CN基团的配位数相同。可以通过考虑[Nb（CN）_8]的配位几何形状的差异来理解TC的差异。使用离散变分（DV）-Xa方法对[Nb〜（IV）（CN）_8]的分子轨道计算表明，十二面体几何形状的桥接N上2p轨道的种群大于方形反棱镜几何形状的2p轨道的种群。计算结果表明，氰基氮上2p轨道的电荷种群会影响NbAC“ NAMn的磁轨道的超交换相互作用，从而决定TC值。

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来源
《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2013年第null期|共5页
作者
Kosuke Nakagawa; Kenta Imoto; Hiroyuki Miyahara; Shin-ichi Ohkoshi;
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正文语种 eng
中图分类无机化学;
关键词
Molecular-based magnet; Manganese(II); Octacyanoniobate; 3D network; Ferrimagnetism; Coordination geometry;

机译：分子基磁体;锰（II）;八氰基铌酸盐;3D网络;铁磁性;配位几何;

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1. Syntheses, crystal structures, and magnetic properties of cyano-bridged Mn(II)-Nb(IV) bimetal assemblies [J] . Kosuke Nakagawa, Kenta Imoto, Hiroyuki Miyahara, Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2013,第Null期

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Syntheses, crystal structures, and magnetic properties of cyano-bridged Mn(II)-Nb(IV) bimetal assemblies

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