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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Structure, magnetism and optical properties of achiral and chiral two-dimensional oxalate-bridged anionic networks with symmetric and asymmetric ammonium cations
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Structure, magnetism and optical properties of achiral and chiral two-dimensional oxalate-bridged anionic networks with symmetric and asymmetric ammonium cations

机译：具有对称和不对称铵阳离子的非手性和手性二维草酸酯桥联阴离子网络的结构，磁性和光学性质

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摘要

A series of two-dimensional (2D) oxalate-based compounds, namely [N(n-C4H9)(4)][(MCrIII)-Cr-II(ox)(3)] (M-II = Mn, Fe; ox = C2O42-) and [N(C2H5)(n-C3H7)(n-C4H9)(n-C5H11)][(MMIII)-M-II(ox)(3)] ((M-II, M-III) = ( Mn, Cr), (Fe, Cr), (Mn, Fe)) were synthesised starting from racemic tris(oxalato) metalate: rac-[M-III(ox)(3)](3-) (M-III = Cr, Fe). For Cr-III, the synthesis has been undertaken starting from resolved (Delta)- or (Lambda)-[Cr-III(ox)(3)](3-). The natural circular dichroism measurements assess the enantioselectivity of the synthesis. X-Ray powder diffraction analysis has revealed that, when racemic reagents are used to synthesise Mn-II containing compounds, a R3c achiral space group is found. In contrast a P6(3) chiral space group is found when starting from (Delta)- or (Lambda)-[ CrIII(ox)(3)](3-). Surprisingly, whatever the optical purity of the starting building block, all FeII containing compounds crystallise in the P63 chiral space group. The magnetic properties of the synthesised compounds confirm that these compounds are ferromagnets for MIII = Cr. For MII = Mn, H ranges between 9 and 11 K and T-c equals 6 K. For M-II = Fe, Theta ranges between 14 and 16 K and T-c between 11 and 12 K. [N(C2H5)(n-C3H7)(n-C4H9)(n- C5H11)][(MnFeIII)-Fe-II(ox)(3)] is an antiferromagnet with Theta = - 107 K and T-N = 29 K.
机译：一系列基于二维（2D）草酸盐的化合物，即[N（n-C4H9）（4）] [（MCrIII）-Cr-II（ox）（3）]（M-II = Mn，Fe; ox = C2O42-）和[N（C2H5）（n-C3H7）（n-C4H9）（n-C5H11）] [（MMIII）-M-II（ox）（3）]（（M-II，M- III）=（Mn，Cr），（Fe，Cr），（Mn，Fe））从外消旋的三（草酸）金属化物开始合成：rac- [M-III（ox）（3）]（3-）（ M-III ＝ Cr，Fe）。对于Cr-III，已经从拆分的Δ-或λ-[Cr-III（ox）（3）]（3-）开始进行合成。天然的圆二色性测量可评估合成的对映选择性。 X射线粉末衍射分析表明，当使用外消旋试剂合成含Mn-II的化合物时，发现了一个R3c非手性空间基团。相反，当从Δ-或λ-[CrIII（ox）（3）]（3-）开始时，发现了P6（3）手性空间基团。出乎意料的是，无论起始构件的光学纯度如何，所有含FeII的化合物都在P63手性空间基团中结晶。合成化合物的磁性能证实，对于MIII = Cr，这些化合物是铁磁体。对于MII = Mn，H范围在9和11 K之间，Tc等于6K。对于M-II = Fe，Theta范围在14和16 K之间，Tc在11和12 K之间。[N（C2H5）（n-C3H7） （n-C4H9）（n-C5H11）] [（MnFeIII）-Fe-II（ox）（3）]是反铁磁体，θ=-107 K，TN = 29K。

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