Elimination-Fusion Self-Assembly of a Nanometer-Scale 72-Nucleus Silver Cluster Caging a Pair of [EuW10O36](9-) Polyoxometalates
Elimination-Fusion Self-Assembly of a Nanometer-Scale 72-Nucleus Silver Cluster Caging a Pair of [EuW10O36](9-) Polyoxometalates
复制标题
笼罩一对 [EuW10O36](9-) 多金属氧酸盐的纳米级 72 核银簇的消除融合自组装
DOI：
10.1002/chem.201705264
复制
发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Zheng Lan-Sun
中科院分区：
文献类型：
--
作者：
Zhang Shan-Shan;Su Hai-Feng;Wang Zhi;Wang Xing-Po;Chen Wen-Xian;Zhao Quan-Qin;Tung Chen-Ho;Sun Di;Zheng Lan-Sun
在溶剂热条件下分离并表征了已知的最大的多金属氧酸盐银炔基团簇[(EuW10O36)2@Ag72(TbUC≡C)48Cl2⋅4 BF4](SD/Ag20)。经单晶X-射线衍射仪(SCXRD)确证为{EuW10}2-in-{Ag72}簇内棒状化合物。高分辨电喷雾电离质谱仪(HR-ESI-MS)表明，这种双阴离子模板簇合物是由溶液中关键的单一阴离子模板Ag42中间体组装而成的。Ag42物种(SD/Ag21)的晶化过程，以及随后的SCXRD分析，对SD/Ag20在溶液中的组装路线提供了重要线索：Ag42团簇横向消除了6个银原子，然后在空位面上融合在一起形成最终的Ag72团簇(消除-融合机制)。[EuW10O36]9−的特征发射在INSD/Ag20中保持得很好。这一工作不仅为大尺寸银团簇的合成以及银团簇与POMS的功能集成提供了一种新的方法，而且对高核银团簇的组装机理也有了深刻的认识。
The largest known polyoxometalate (POM)‐templated silver‐alkynyl cluster, [(EuW10O36)2@Ag72(tBuC≡C)48Cl2⋅4 BF4] (SD/Ag20), was isolated under solvothermal conditions and structurally characterized. It was confirmed by single‐crystal X‐ray diffraction (SCXRD) as a {EuW10}2‐in‐{Ag72} clusters‐in‐cluster rod‐like compound. The high‐resolution electrospray ionization mass spectrometry (HR‐ESI‐MS) shows that such a double anion‐templated cluster is assembled from a crucial single anion‐templated Ag42intermediate in the solution. The crystallization of Ag42species (SD/Ag21), followed by SCXRD, gave an important clue about the assembly route ofSD/Ag20in solution: the Ag42cluster eliminates six silver atoms laterally, then fuses together at the vacant face to form the final Ag72cluster (elimination‐fusion mechanism). The characteristic emission of [EuW10O36]9−is well maintained inSD/Ag20. This work not only provides a new method for the synthesis of larger silver clusters as well as the functional integration of the silver cluster and POMs, but also gives deep insights about the high‐nuclear silver cluster assembly mechanism.