Solvothermal exploration of the As, V, Mn reaction system in the presence of aqueous diethylenetriamine (=dien) solution led to the discovery of [Mn^II₄V^IV₁₂As^III₈O₄₀(dien)₄(H₂O)] ⋅ 3.5H₂O, containing the first arsenato-polyoxovanadate featuring a {Mn₂V₁₂As₈O₄₀} cluster shell. In comparison to its parental {V₁₄As₈O₄₂} archetype, two vanadyl (VO²⁺) units at opposite ends of the polyoxovanadate shell here are substituted by Mn²⁺ centers. In the solid state, these {Mn₂V₁₂As₈O₄₀} units are joined into rods by sharing common Mn−O−V linkages. Expansion of the cluster shell by two further Mn²⁺ sites via Mn−O=V bridges generates a {Mn₄V₁₂As₈O₄₀} moiety. Three Mn²⁺ cations are joined by monodentate-coordinating dien ligands, which link the rods into layers. The dien ligands here coexist in three different coordination modes: monodentate, bidentate and tridentate, which is rarely observed. Magnetic susceptibility measurements show the expected significant antiferromagnetic coupling interactions between all spin centers present in the title compound, namely the isotropic spin-5/2 Mn²⁺ centers and the isotropic spin-1/2 vanadyl groups, in line with most other heterometal-substituted arsenato-polyoxovanadate(IV) clusters.

中文翻译：

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{V14As8} 多氧钒酸盐原型内的 Mn2+ 取代导致 {Mn2V12As8} 壳具有异金属位置的转位

在二亚乙基三胺 (=dien) 水溶液存在下对 As、V、Mn 反应体系进行溶剂热探索，发现了 [Mn ^II ₄ V ^IV ₁₂ As ^III ₈ O ₄₀ (dien) ₄ (H ₂ O)] ⋅ 3.5H ₂ O，包含第一个具有 {Mn ₂ V ₁₂ As ₈ O ₄₀ } 簇壳的砷酸-多氧钒酸盐。与其亲本 {V ₁₄ As ₈ O ₄₂ } 原型相比，两个氧钒基 (VO ²⁺)此处聚氧钒酸盐壳相对端的单元被Mn ²⁺中心取代。在固态下，这些 {Mn ₂ V ₁₂ As ₈ O ₄₀ } 单元通过共享公共 Mn-O-V 键连接成棒。通过 Mn-O=V 桥由两个另外的 Mn ²⁺位点扩展簇壳产生 {Mn ₄ V ₁₂ As ₈ O ₄₀ } 部分。三锰²⁺阳离子通过单齿配位二烯配体连接，将杆连接成层。这里的二烯配体以三种不同的配位模式共存：单齿、双齿和三齿，这很少被观察到。磁化率测量表明，标题化合物中存在的所有自旋中心（即各向同性自旋 5/2 Mn ²⁺中心和各向同性自旋 1/2 氧钒基）之间存在预期的显着反铁磁耦合相互作用，这与大多数其他异质金属-取代的砷酸-多氧钒酸盐 (IV) 簇。