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 Ce<sub>10sub>-cluster-embedded polyoxotungstate (POT) (TMA)<sub>14sub>H<sub>2sub>[Ce<sup>IIIsup>(H<sub>2sub>O)<sub>6sub>]{[Ce<sup>IVsup><sub>7sub>Ce<sup>IIIsup><sub>3sub>O<sub>6sub>(OH)<sub>6sub>(CO<sub>3sub>)(H<sub>2sub>O)<sub>11sub>][(P<sub>2sub>W<sub>16sub>O<sub>59sub>)]<sub>3sub>}·41H<sub>2sub>O (1) (TMA = tetramethyleneamine) by coordination-driven self-assembly strategy, which contains the largest Ce cluster [Ce<sup>IVsup><sub>7sub>Ce<sup>IIIsup><sub>3sub>O<sub>6sub>(OH)<sub>6sub>(CO<sub>3sub>)(H<sub>2sub>O)<sub>11sub>] (Ce<sub>10sub>) in all the Ln-containing POM chemistry to date. Self-assembly of the in situ dilacunary [P<sub>2sub>W<sub>16sub>O<sub>59sub>]<sup>12–sup> fragments and mixed Ce<sup>3+sup> and Ce<sup>4+sup> ions by means of coordination-driven force results in a novel 2D graphite-like framework constructed from mixed-valent cerium(III/IV) cluster {Ce<sub>10sub>} encapsulated poly(POT) units and Ce<sup>3+sup> ions. The most remarkable feature is that the skeleton of the centrosymmetric Ce<sub>10sub>-cluster-embedded POT trimer contains three dilacunary [P<sub>2sub>W<sub>16sub>O<sub>59sub>]<sup>12–sup> fragments trapping a novel {Ce<sub>10sub>} cluster via 18 terminal-oxo and three μ<sub>4sub>-oxo atoms.