The integration of lanthanide(Ln)ions and polyoxoniobates(PONbs)is challenging,and the know Ln-substituted PONbs are still scarce.This work introduces high-nuclear iso-Ln-oxo clusters into th PONb system.The first ser...The integration of lanthanide(Ln)ions and polyoxoniobates(PONbs)is challenging,and the know Ln-substituted PONbs are still scarce.This work introduces high-nuclear iso-Ln-oxo clusters into th PONb system.The first series of high-nuclear Ln-oxo clusters encapsulated heterometallic polyoxonio bates H_9[Na(H_(2)O)_(4)][Cu(en)_(2)]_(10){Ln_6(μ_(3)-OH)_6(Si Nb_(18)O_(54))_(3)}·18H_(2)O(1-Ln,en=ethylenediamine,Ln=Dy,Gd Tb,Ho,Er,Tm,Yb,Lu)based on flower-like{Ln_(6)(μ_(3)-OH)_(6)(Si Nb_(18)O_(54))_(3)}({Ln_6Si_(3)Nb_(54)})clusters hav been successfully synthesized via one-pot hydrothermal synthesis strategy.The flower-like polyoxoanio{Ln_6Si_(3)Nb_(54)}is consisted of three heteropolyoxoniobate{Si Nb_(18)O_(54)}clusters and one unique planar equ lateral triangle-shaped{Ln_6(μ_(3)-OH)_6}cluster,which presents the highest nuclear iso-Ln-oxo cluster i PONb chemistry.In{Ln_6(μ_(3)-OH)_6}cluster,each pair ofμ_(3)-OH groups link three Dy^(3+)ions to form a sma approximate equilateral triangle-shaped{Dy_(3)(OH)_(2)}cluster.Furthermore,the three{Dy_(3)(OH)_(2)}cluster comprise a bigger approximate equilateral triangle-shaped{Dy_6(μ_(3)-OH)_6}cluster.The reported hexanu clear{Ln_6}cluster skeletons are mostly octahedral,however,such equilateral triangle-shaped skeleton o the hexanuclear Ln-oxo cluster is first observed.The 1-Dy exhibits good water vapor adsorption capacit and ferromagnetic properties.展开更多
Although the synthesis of giant lanthanide(Ln)-containing polyoxotungstates(POTs)has long been actively pursued,it remains challenging to encapsulate high-nuclearity Ln–O clusters in POT shells because of the highly ...Although the synthesis of giant lanthanide(Ln)-containing polyoxotungstates(POTs)has long been actively pursued,it remains challenging to encapsulate high-nuclearity Ln–O clusters in POT shells because of the highly complicated assembly process.This work demonstrates a simple synthetic strategy of using lacunary POT precursors to assemble with in situ generated Ln–O clusters in the presence of basic N-containing ligands,which exert a slow-releasing effect for Ln^(3+)ions in alkaline conditions.展开更多
A Keggin-type polyoxomolybdate[H2biim]{Ni(biim)3(SiMO12O40)}[biim =1H,1'H-[2,2']biimidazolyl]has been synthesized under hydrothermal condition and characterized by XRD,temperature-dependent IR,TG,temperature-ind...A Keggin-type polyoxomolybdate[H2biim]{Ni(biim)3(SiMO12O40)}[biim =1H,1'H-[2,2']biimidazolyl]has been synthesized under hydrothermal condition and characterized by XRD,temperature-dependent IR,TG,temperature-induced and magnetism-induced 2D infrared correlation spectroscopy(2D-IR COS)and UV-vis DRS in order to explore the relationship between structure and properties.Temperatureinduced 2D-IR COS spectroscopy indicates that the terminal Mo-Oμ/υbonds are more sensitive than the bridging Mo=Ot,bands to temperature variation,which is in agreement with the conclusion of temperature-dependent IR.Magnetism-dependent 2D-IR COS spectroscopy reveals the stretching vibration of the Mo=Ot,occurs prior to the stretching vibration of the Mo-Oμ/υ,which is due to the coordination environment and the valence of the Si atom.The stability of compound 1 is investigated via TG and temperature-dependent IR.In RhB degradation,compound 1 shows good photocatalytic abilities.展开更多
基金financial support from the National Natural Science Foundation of China (NSFC, Nos. 21971040, 21971039 and 21773029)。
文摘The integration of lanthanide(Ln)ions and polyoxoniobates(PONbs)is challenging,and the know Ln-substituted PONbs are still scarce.This work introduces high-nuclear iso-Ln-oxo clusters into th PONb system.The first series of high-nuclear Ln-oxo clusters encapsulated heterometallic polyoxonio bates H_9[Na(H_(2)O)_(4)][Cu(en)_(2)]_(10){Ln_6(μ_(3)-OH)_6(Si Nb_(18)O_(54))_(3)}·18H_(2)O(1-Ln,en=ethylenediamine,Ln=Dy,Gd Tb,Ho,Er,Tm,Yb,Lu)based on flower-like{Ln_(6)(μ_(3)-OH)_(6)(Si Nb_(18)O_(54))_(3)}({Ln_6Si_(3)Nb_(54)})clusters hav been successfully synthesized via one-pot hydrothermal synthesis strategy.The flower-like polyoxoanio{Ln_6Si_(3)Nb_(54)}is consisted of three heteropolyoxoniobate{Si Nb_(18)O_(54)}clusters and one unique planar equ lateral triangle-shaped{Ln_6(μ_(3)-OH)_6}cluster,which presents the highest nuclear iso-Ln-oxo cluster i PONb chemistry.In{Ln_6(μ_(3)-OH)_6}cluster,each pair ofμ_(3)-OH groups link three Dy^(3+)ions to form a sma approximate equilateral triangle-shaped{Dy_(3)(OH)_(2)}cluster.Furthermore,the three{Dy_(3)(OH)_(2)}cluster comprise a bigger approximate equilateral triangle-shaped{Dy_6(μ_(3)-OH)_6}cluster.The reported hexanu clear{Ln_6}cluster skeletons are mostly octahedral,however,such equilateral triangle-shaped skeleton o the hexanuclear Ln-oxo cluster is first observed.The 1-Dy exhibits good water vapor adsorption capacit and ferromagnetic properties.
基金support from the NSFs of China(grant nos.21773029,21971039,and 22171045).
文摘Although the synthesis of giant lanthanide(Ln)-containing polyoxotungstates(POTs)has long been actively pursued,it remains challenging to encapsulate high-nuclearity Ln–O clusters in POT shells because of the highly complicated assembly process.This work demonstrates a simple synthetic strategy of using lacunary POT precursors to assemble with in situ generated Ln–O clusters in the presence of basic N-containing ligands,which exert a slow-releasing effect for Ln^(3+)ions in alkaline conditions.
基金financially supported by the National Natural Science Foundation of China(No.51373003)Beijing Natural Science Foundation(No.2122059)Open Fund of State Key Laboratory of Structural Chemistry(No.20130015) and Science
文摘A Keggin-type polyoxomolybdate[H2biim]{Ni(biim)3(SiMO12O40)}[biim =1H,1'H-[2,2']biimidazolyl]has been synthesized under hydrothermal condition and characterized by XRD,temperature-dependent IR,TG,temperature-induced and magnetism-induced 2D infrared correlation spectroscopy(2D-IR COS)and UV-vis DRS in order to explore the relationship between structure and properties.Temperatureinduced 2D-IR COS spectroscopy indicates that the terminal Mo-Oμ/υbonds are more sensitive than the bridging Mo=Ot,bands to temperature variation,which is in agreement with the conclusion of temperature-dependent IR.Magnetism-dependent 2D-IR COS spectroscopy reveals the stretching vibration of the Mo=Ot,occurs prior to the stretching vibration of the Mo-Oμ/υ,which is due to the coordination environment and the valence of the Si atom.The stability of compound 1 is investigated via TG and temperature-dependent IR.In RhB degradation,compound 1 shows good photocatalytic abilities.