Self-assembly and structural transformations of high-nuclearity palladium-rich polyoxometalates
Self-assembly and structural transformations of high-nuclearity palladium-rich polyoxometalates
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DOI：
10.1039/c3qi00075c
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发表时间：
2014-01-01
影响因子：
7
通讯作者：
Cronin, Leroy
中科院分区：
文献类型：
--
作者：
Cameron, Jamie M.;Gao, Jing;Cronin, Leroy
利用Se-IV和Te-IV杂原子的结构导向效应的一锅法策略已经产生了迄今为止最高的含核贵金属的聚氧六环酸盐;包括富钯硒钨酸盐异构体K-28[H12 Pd 10 Se 10 W52 O206]中心点65 H（2）O（1）和K-26[H14 Pd 10 Se 10 W52 O206]中心点68 H（2）O（2），和纳米级碲钨酸盐团簇Na-40[Pd 6 Te 19 W 42 O 190]中心点76 H（2）O（3）。这些反应体系表现出显着的结构灵活性，并指向一个新的路线走向复杂的杂金属物种的合成，其中多个空缺的多聚氧杂环戊二烯酸盐的“积木”已组装到捕获一个瞬态oxopalladate物种怀疑发挥作用，在几个常见的多聚氧钯酸盐的组装。质谱已被应用于探索和比较化合物1-3的溶液稳定性，证明Se-IV和Te-IV模板系统的显著不同的性质。已经提供了1的电化学分析，并且由Pd氧化还原过程主导，其中簇的还原导致Pd金属的电沉积，并观察随后形成的PdO物质，与先前报道的含氧代钯酸盐的物质同时发生。
A one-pot strategy exploiting the structure directing effects of Se-IV and Te-IV heteroatoms has yielded the highest nuclearity noble metal containing polyoxometalates to date; including the palladium-rich seleno-tungstate isomers K-28[H12Pd10Se10W52O206]center dot 65H(2)O (1) and K-26[H14Pd10Se10W52O206]center dot 68H(2)O (2), and the nanoscale tellurotungstate cluster Na-40[Pd6Te19W42O190]center dot 76H(2)O (3). These reaction systems exhibit remarkable structural flexibility and point to a new route towards the synthesis of complex heterometallic species, in which multiple lacunary polyoxometalate 'building blocks' have been assembled to trap a transient oxopalladate species suspected to play a role in the assembly of several common polyoxopalladates. Mass spectrometry has been applied to explore and compare the solution stability of compounds 1-3, demonstrating the markedly different properties of the Se-IV and Te-IV templated systems. Electrochemical analysis of 1 has been provided and is dominated by Pd redox processes, with reduction of the cluster resulting in electrodeposition of Pd metal and observation of the subsequent formation of PdO species, concurrent with previously reported oxopalladate containing species.