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,whi...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.展开更多
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)。
文摘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.
