A Gadolinium-Bridged Polytungstoarsenate(III) Nanocluster: [Gd8As12W124O432(H2O)22]60-
A Gadolinium-Bridged Polytungstoarsenate(III) Nanocluster: [Gd8As12W124O432(H2O)22]60-
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DOI：
10.1002/anie.200903299
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发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
Patzke, Greta R.
中科院分区：
文献类型：
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作者：
Hussain, Firasat;Conrad, Franziska;Patzke, Greta R.
聚氧丙烯酸盐（POM：高氧化态过渡金属的大分子氧簇）[1-3]在结构多功能性和在例如医学、催化、多功能材料、成像以及生物和纳米技术中的潜在应用方面是无与伦比的。[4-16]在众多的聚氧乙烯酸盐结构基序中，含镧系元素的POM提供了特别有趣的特征，例如磁性、发光、刘易斯酸催化以及从Gd-POM开发磁共振成像（MRI）造影剂。[17]具有高碱性氧原子的缺位POM与大的亲氧镧系元素阳离子的合成组合是形成具有大量金属中心或扩展的金属-氧框架的分子多氧阴离子络合物的有力策略。自从1971年第一个含镧系元素的多金属氧化合物被报道以来，[18]许多其他的研究小组一直致力于开发这样的簇（例如Pope，Müller，Francesconi，Yamase，Krebs，Gouzerh，Saucheresse和Kortz;详细的调查，见支持信息，表S1）。[19]含铈的多钨砷酸盐-（III），[Ce 16 As 12（H2O）36 W148 O 524] 76 O 5，得自Pope埃塔尔，仍然是已知的最大的多钨酸盐，[20]其次是我们之一发表的含二甲基锡的W108物种。[21]在此，我们介绍了含镧系元素的纳米簇[Gd 8As 12 W124 O 432（H2O）22] 60 [1]，作为迄今为止报道的第二大多钨酸盐。
Polyoxometalates (POMs: macromolecular oxoclusters of transition metals in high oxidation states)[1–3] are unmatched in terms of structural versatility and potential applications in for example medicine, catalysis, multifunctional materials, imaging, and bio-and nanotechnology.[4–16] Amongst the multitude of polyoxometalate structural motifs, the lanthanoid-containing POMs offer particularly interesting features, such as magnetism, luminescence, Lewis acid catalysis, and the development of magnetic resonance imaging (MRI) contrast agents from Gd-POMs.[17] The synthetic combination of a lacunary POM with highly basic oxygen atoms with large oxophilic lanthanoid cations is a powerful strategy to form molecular polyoxoanion complexes with a large number of metal centers or extended metal–oxygen frameworks. Since the first lanthanoid-containing POMs were reported in 1971,[18] many other groups have been working on the development of such clusters (for example Pope, Müller, Francesconi, Yamase, Krebs, Gouzerh, SØcheresse, and Kortz; for a detailed survey, see the Supporting Information, Table S1).[19] The cerium-containing polyoxotungstoarsenate-(III),[Ce16As12 (H2O) 36W148O524] 76À from Pope etal., still remains the largest polyoxotungstate known,[20] followed by the dimethyltin-containing W108 species published by one of us.[21] Herein, we present the lanthanoid-containing nanocluster [Gd8As12W124O432 (H2O) 22] 60À (1) as the second-largest polyoxotungstate reported to date.