Unraveling the condensation reactions of heterometallic {BiNb_(4)} moieties into hybrid Bi_(x)Nb_(y)-oxo clusters with mass spectrometry  

作　　者：Lv-Bing Yuan Ya-Yong Sun Jian Zhang Lei Zhang 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Science China Chemistry》2021年第3期413-418,共6页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21922111 and 91961108);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)。

摘　　要：The most effective methodologies for the construction of polynuclear complexes usually take advantage of preorganized building blocks.Herein,we successfully developed a new versatile heterometallic{BiNb_(4)}moiety,which can be applied for the assembly of less explored organic-inorganic hybrid polyoxoniobates.Through controlled condensation reactions,three{BiNb_(4)}moieties can be assembled into a pair of isomeric Bi_(3)Nb_(18)clusters at different temperatures;whilst four{BiNb_(4)}moieties can be combined into two unique Bi_(4)Nb_(16)and Bi_(4)Nb_(18)tetramers in different solvents.Interestingly,we have used mass spectrometry to probe the above condensation reactions,which clearly confirmed a stepwise bottom-up assembly process by capturing the presence of bismuth subsalicylate precursors,salicylate coordinated intermediates,Nb incorporated{BiNb_(4)}moieties and the final Bi_(x)Nb_(y)-oxo clusters,respectively.Moreover,the packing modes of the{BiNb_(4)}units induce different solution behaviors,and the{BiNb_(4)}units in Bi4Nb16can be recombined by post-synthetic recrystallization in acetonitrile to produce a new tetramer Bi_(4)Nb_(18)-R.Therefore,this work provides not only a useful{BiNb_(4)}building unit but also the mechanism for their condensation,both of which will promote the future development of metal-oxo clusters.

关 键 词：cluster compounds mass spectrometry heterometallic complexes condensation reactions 

分 类 号：O641.4[理学—物理化学] O657.63[理学—化学]