Design and synthesis of "dumb-bell" and "triangular" inorganic-organic hybrid nanopolyoxometalate clusters and their characterisation through ESI-MS analyses.
Design and synthesis of "dumb-bell" and "triangular" inorganic-organic hybrid nanopolyoxometalate clusters and their characterisation through ESI-MS analyses.
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DOI：
10.1002/chem.201100257
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发表时间：
2011-06
期刊：
影响因子：
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通讯作者：
C. Pradeep;Fengyan Li;C. Lydon;H. Miras;D. Long;Lin Xu;L. Cronin
中科院分区：
文献类型：
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作者：
C. Pradeep;Fengyan Li;C. Lydon;H. Miras;D. Long;Lin Xu;L. Cronin
合成了一系列基于三羟甲基氨基甲烷（TRIS）的线型（bis（TRIS））和三角形（tris（TRIS））配体，并将其共价连接到Wells-Dawson型簇合物[P（2）V（3）W（15）O（62）]（9-）上，得到了一系列纳米级无机-有机杂化聚氧乙烯簇合物。这些巨大的杂交体，具有类似的分子量的小蛋白质的范围内的100 - 16 kDa，明确地通过使用高分辨率ESI-MS的特征。这些化合物的ESI-MS光谱显示，在负离子模式，显示不同的峰组对应于不同的阴离子电荷状态，从3（-）至8（-）的杂交体。这些单独组中的每个峰可以明确地归属于具有四丁基铵（TBA）和其他阳离子的不同组合的相应混合簇阴离子。因此，这项研究突出了高分辨率ESI-MS的强大功能，用于明确表征具有巨大质量（10 - 16 kDa）的大型纳米级无机-有机混合簇。此外，这些化合物的设计合成指出了这样一个事实，即我们能够通过配体设计路线在这些无机-有机杂化聚氧乙烯酸酯（POM）的合成中实现大量的结构预设计，这在传统的"一锅法" POM合成中通常是不可能的。
A series of tris(hydroxymethyl)aminomethane (TRIS)-based linear (bis(TRIS)) and triangular (tris(TRIS)) ligands has been synthesised and were covalently attached to the Wells-Dawson type cluster [P(2)V(3)W(15)O(62)](9-) to generate a series of nanometer-sized inorganic-organic hybrid polyoxometalate clusters. These huge hybrids, with a molecular mass similar to that of small proteins in the range of ≈10-16 kDa, were unambiguously characterised by using high-resolution ESI-MS. The ESI-MS spectra of these compounds revealed, in negative ion mode, a characteristic pattern showing distinct groups of peaks corresponding to different anionic charge states ranging from 3(-) to 8(-) for the hybrids. Each peak in these individual groups could be unambiguously assigned to the corresponding hybrid cluster anion with varying combinations of tetrabutylammonium (TBA) and other cations. This study therefore highlights the prowess of the high-resolution ESI-MS for the unambiguous characterisation of large, nanoscale, inorganic-organic hybrid clusters that have huge mass, of the order of 10-16 kDa. Also, the designed synthesis of these compounds points to the fact that we were able to achieve a great deal of structural pre-design in the synthesis of these inorganic-organic hybrid polyoxometalates (POMs) by means of a ligand design route, which is often not possible in traditional "one-pot" POM synthesis.