Coordination-Driven Self-Assembly of a 2D Graphite-Like Framework Constructed from High-Nuclear Ce10 Cluster Encapsulated Polyoxotungstates

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• 作者：Pengtao Ma ; Rong Wan ; Yueyan Wang ; Feng Hu ; Dongdi Zhang ; Jingyang Niu ; Jingping Wang
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：January 19, 2016
• 年：2016
• 卷：55
• 期：2
• 页码：918-924
• 全文大小：522K
• ISSN：1520-510X

文摘

It is challenging to explore and prepare high-nuclear lanthanide (Ln) cluster-encapsulated polyoxometalates (POMs). Herein, we fabricate an unprecedented Ce₁₀-cluster-embedded polyoxotungstate (POT) (TMA)₁₄H₂[Ce^III(H₂O)₆]{[Ce^IV₇Ce^III₃O₆(OH)₆(CO₃)(H₂O)₁₁][(P₂W₁₆O₅₉)]₃}·41H₂O (1) (TMA = tetramethyleneamine) by coordination-driven self-assembly strategy, which contains the largest Ce cluster [Ce^IV₇Ce^III₃O₆(OH)₆(CO₃)(H₂O)₁₁] (Ce₁₀) in all the Ln-containing POM chemistry to date. Self-assembly of the in situ dilacunary [P₂W₁₆O₅₉]^12– fragments and mixed Ce³⁺ and Ce⁴⁺ ions by means of coordination-driven force results in a novel 2D graphite-like framework constructed from mixed-valent cerium(III/IV) cluster {Ce₁₀} encapsulated poly(POT) units and Ce³⁺ ions. The most remarkable feature is that the skeleton of the centrosymmetric Ce₁₀-cluster-embedded POT trimer contains three dilacunary [P₂W₁₆O₅₉]^12– fragments trapping a novel {Ce₁₀} cluster via 18 terminal-oxo and three μ₄-oxo atoms.