Unraveling the condensation reactions of heterometallic {BiNb4} moieties into hybrid BixNby-oxo clusters with mass spectrometry

• 作者: Lv-Bing Yuan Ya-Yong Sun Jian Zhang Lei Zhang
• 来源期刊: 中国科学：化学（英文版）
• 年，卷（期）: 2021,（3）
• 所属期刊栏目: ARTICLES
• 页码范围: 413-418
• 页数: 6页
• 语种: 英文

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 {BiNb4} moiety,which can be applied for the assembly of less explored organic-inorganic hybrid polyoxoniobates.Through controlled condensation reactions,three {BiNb4} moieties can be assembled into a pair of isomeric Bi3Nb18 clusters at different temperatures;whilst four {BiNb4} moieties can be combined into two unique Bi4Nb16 and Bi4Nb18 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 {BiNb4} moieties and the final BixNby-oxo clusters,respectively.Moreover,the packing modes of the {BiNb4} units induce different solution behaviors,and the {BiNb4} units in Bi4Nb16 can be recombined by post-synthetic recrystallization in acetonitrile to produce a new tetramer Bi4Nb18-R.Therefore,this work provides not only a useful {BiNb4} building unit but also the mechanism for their condensation,both of which will promote the future development of metal-oxo clusters.