A new high-nuclear Ti-oxo-cluster-added poly(polyoxometalate) Cs₂Na₁₉H₁₂[(Cs@Ti₁₂O₁₈)@{(A-α-SiW₉O₃₄) (P₂W₁₅O₅₆)₃}]·29H₂O (1) has been made by reacting two types of trivacant precursors with TiOSO₄ under hydrothermal conditions. The polyoxoanion of 1 contains one Keggin-type [A-α-SiW₉O₃₄]^10– and three Dawson-type [P₂W₁₅O₅₆]^12– fragments that synergistically induce the Ti⁴⁺ ions to aggregate at vacant sites, resulting in a large {Ti₁₂}-oxo-cluster cavity sealing a Cs⁺ ion. It is worth noting that the {Ti₁₂} cluster is built by three edge-shared Ti₃O₁₃ ({Ti₃}¹) cores and one corner-shared Ti₃O₁₅ ({Ti₃}²) core bridged via 6 μ₂-O, which has never been seen before in polyoxometalate chemistry. Significantly, 1 represents the first example of [A-α-SiW₉O₃₄]^10– and [P₂W₁₅O₅₆]^12– simultaneously participating in making poly(polyoxometalate).

中文翻译：

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{Ti12} 簇添加聚（多金属氧酸盐）含有混合的 Trivacant Keggin 和 Dawson 片段

一种新型高核 Ti-oxo-cluster 添加聚（多金属氧酸盐）Cs ₂ Na ₁₉ H ₁₂ [(Cs@Ti ₁₂ O ₁₈ )@{( A -α-SiW ₉ O ₃₄ ) (P ₂ W ₁₅ O ₅₆ ) ₃ }]·29H ₂ O ( 1 ) 是通过在水热条件下将两种类型的三空基前体与TiOSO ₄反应制备的。1的多氧阴离子包含一个 Keggin 型 [ A -α-SiW ₉ O ₃₄ ] ^10–和三个 Dawson 型 [P₂ W ₁₅ O ₅₆ ] ^12–碎片协同诱导 Ti ⁴⁺离子聚集在空位，导致大的 {Ti ₁₂ }-氧簇腔密封 Cs ⁺离子。值得注意的是，{Ti ₁₂ } 簇由三个共享边的 Ti ₃ O ₁₃ ({Ti ₃ } ¹ ) 核和一个共享角的 Ti ₃ O ₁₅ ({Ti ₃ } ² ) 核通过 6 桥接而成μ ₂ -O，以前在多金属氧酸盐化学中从未见过。值得注意的是，1代表[ A -α-SiW ₉ O ₃₄ ] ^10–和[P ₂ W ₁₅ O ₅₆ ] ^12–同时参与制造聚（多金属氧酸盐）的第一个例子。