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首页> 外文期刊>Journal of Physics, D. Applied Physics: A Europhysics Journal >Crystal structures of hexacyanometallates with bifurcated cyano groups
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Crystal structures of hexacyanometallates with bifurcated cyano groups

机译：具有分叉氰基的六氰基金属盐的晶体结构

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摘要

The crystal structures for T-2[M(CN)(6)] where T = Mn, Cd; M = Fe, Ru, Os, were refined from the corresponding XRD powder patterns using the Rietvelwd method in the hexagonal P-3 (147) space group with Z = 1. In the structure of these families of anhydrous hexacyanometallates (II) the N end of the CN group appears bifurcated, serving as a ligand for two neighbouring T metals. Such a coordination mode has not been reported before for transition metal hexacyanometallates but it is consistent with the magnetic properties and Mossbauer, IR and Raman spectra of the studied compounds. The anhydrous solids are obtained by dehydration of the corresponding octahydrates. In the hydrated form the metals (Mn, Cd) linked at the N ends have a mixed coordination sphere formed by three N atoms and three coordinated waters, with two of these latter forming bridges between two neighbouring metals. The loss of these structural waters leaves the metals (T) in an unstable state with only three ligands in their coordination sphere and a structural transformation involving a change in the CN group electronic configuration is induced. The metal coordination through bifurcated CN groups leads to a remarkable increase in the charge overlapping between the metal centres, which appears attractive for molecular magnet design.
机译：T-2 [M（CN）（6）]的晶体结构，其中T = Mn，Cd;在Z = 1的六边形P-3（147）空间群中，使用Rietvelwd方法从相应的XRD粉末图案中精制出M = Fe，Ru，Os。在这些无水六氰基金属盐（II）族的结构中CN基团的末端看起来是分叉的，充当两个相邻T金属的配体。对于过渡金属六氰基金属酸盐，以前尚未报道过这种配位模式，但与所研究化合物的磁性和Mossbauer，IR和拉曼光谱是一致的。通过脱水相应的八水合物获得无水固体。在水合形式下，在N端连接的金属（Mn，Cd）具有由三个N原子和三个配位水形成的混合配位球，其中两个后者形成了两个相邻金属之间的桥。这些结构水的损失使金属（T）处于不稳定状态，在它们的配位域中只有三个配体，并且诱导了涉及CN基团电子构型变化的结构转变。通过分叉的CN基团进行的金属配位导致金属中心之间的电荷重叠显着增加，这似乎对分子磁体设计有吸引力。

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