Sodium Transition Metal Vanadates from Hydrothermal Brines: Synthesis and Characterization of NaMn4(VO4)3, Na2Mn3(VO4)3, and Na2Co3(VO4)2(OH)2,European Journal of Inorganic Chemistry

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Sodium Transition Metal Vanadates from Hydrothermal Brines: Synthesis and Characterization of NaMn4(VO4)3, Na2Mn3(VO4)3, and Na2Co3(VO4)2(OH)2
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-10 , DOI: 10.1002/ejic.202000518
Tiffany M. Smith Pellizzeri ₁ , Gregory Morrison ₂ , Colin D. McMillen ₃ , Hans-Conrad zur Loye ₂ , Joseph W. Kolis ₄

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Three new examples of transition metal vanadates have all been synthesized by a related hydrothermal synthetic route using variations of sodium hydroxide/sodium chloride brines as mineralizers. Compound 1, NaMn₄(VO₄)₃, is built from equivalent interlocking chains of Mn²⁺ edge shared octahedra, further coordinated to one another by (VO₄)^3– vanadate groups to form a three‐dimensional structure. Compound 2, Na₂Mn₃(VO₄)₃, forms a complex three‐dimensional structure of mixed‐valence 2+/3+ manganese edge‐sharing octahedra forming chains, with (VO₄)^3– tetrahedra acting as space‐fillers in the structure. Structure 3, Na₂Co₃(VO₄)₂(OH)₂, is built of a two‐dimensional distorted honeycomb of edge shared Co²⁺ layers decorated by, but not connected by, vanadate groups. The layers bear a relationship to Kagome nets but the structure contains no ideal trigonal symmetry. All compounds were characterized by single‐crystal X‐ray diffraction. Compounds 1 and 3 were characterized by magnetic susceptibility. The magnetic susceptibility of 1 displays the moment characteristic of Mn²⁺ and a transition at 46 K to a spin canted antiferromagnet. Compound 3 shows evidence of spin–orbit coupling in the Co²⁺ ions with antiferromagnetic ordering at 4.4.K and highly anisotropic field‐dependent behavior with multiple metamagnetic transitions.

中文翻译：

水热卤化物中的过渡金属钒酸盐：NaMn4（VO4）3，Na2Mn3（VO4）3和Na2Co3（VO4）2（OH）2的合成与表征

过渡金属钒酸盐的三个新实例均通过相关的水热合成路线合成，使用氢氧化钠/氯化钠盐水的变化作为矿化剂。化合物1 NaMn ₄（VO ₄）₃是由Mn ²⁺边缘共享的八面体的等效互锁链构建的，进一步由（VO ₄）^3-钒酸盐基团相互配位，形成三维结构。化合物2 Na ₂ Mn ₃（VO ₄）₃，形成一个复杂的三维结构，混合价2 + / 3 +锰边共享八面体形成链，其中（VO ₄）^3–四面体在结构中充当空间填充物。结构3 Na ₂ Co ₃（VO ₄）₂（OH）₂由二维扭曲的蜂窝组成，该蜂窝由边缘共用的Co ²⁺层装饰，但不由钒酸盐基团连接。这些层与Kagome网络有关系，但结构不包含理想的三角对称性。所有化合物均通过单晶X射线衍射表征。化合物1和3以磁化率为特征。1的磁化率显示Mn ²⁺的矩特性以及在46 K处转变为自旋倾斜反铁磁体的跃迁。化合物3显示了Co ²⁺离子中自旋轨道耦合的证据，其反铁磁序数为4.4.K，并且具有高度各向异性的场相关行为和多个亚磁跃迁。

更新日期：2020-09-15

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