A novel Ni-capped complex H4{[Ni（H2O）3]2[CeMo12O42] }· 13.5H2O has been synthesized, which is the first Silverton-type anion capped with two Ni units via three terminal oxygen atoms. Crystallographic data for t...A novel Ni-capped complex H4{[Ni（H2O）3]2[CeMo12O42] }· 13.5H2O has been synthesized, which is the first Silverton-type anion capped with two Ni units via three terminal oxygen atoms. Crystallographic data for the title compound： Trigonal, space group R-3, a = 13.0950（19）, b = 13.0950（19）, c = 33.029（7） A, α = β= γ = 58.727（17）A °, V = 4905.1（14） A °^3, Z = 3, Mr= 2437.17, Dc = 2.475 g/cm^3, F（000） = 3462, T = 293（2） K, μ（MoKa） = 3.564 mm^-1, Rt = 0.0369, wR2 = 0.0905 and GOF= 1.079 for 151 parameters and 1963 reflections with I 〉 2σ（I） in the range of 1.85≤θ≤25.50°.展开更多
Polyoxometalates(POMs)are primarily constructed from{MO6}octahedra connected through corner-,edge-,and/or face-sharing modes,with face-sharing being particularly rare.Silverton clusters,characterized by their face-sha...Polyoxometalates(POMs)are primarily constructed from{MO6}octahedra connected through corner-,edge-,and/or face-sharing modes,with face-sharing being particularly rare.Silverton clusters,characterized by their face-sharing{MO6}octahedra,have been reported for Mo and W.However,Nb-based Silverton and polyoxoniobates(PONbs)with face-sharing octahedra have not yet been synthesized,despite their occurrence in natural minerals.Herein,[(Nb_(13)O_(42)){Te_(3)(B-α-TeNb_(9)O_(33))}_(4)](1a)and its trivacant structure[(Nb_(10)O_(36)){Te_(3)(B-α-TeNb_(9)O_(33))}_(4)](2a)with the long-sought feature of face-sharing{NbO_(6)}octahedra have been synthesized for the first time.In 1a,the central{Nb_(13)O_(42)},consisting of six sets of face-sharing{Nb_(2)O_(9)}and a central Nb,is surrounded by 12 Te(IV)ions anchored on four{TeNb_(9)O_(33)}.Notably,the observed{Nb_(13)O_(42)}can be viewed as both a synthetic analogue of natural minerals and a topological isomer of the classic Silverton cluster.Moreover,small angle X-ray scattering data analysis confirms the formation of the targeted PONb cluster and determines the co-existing key cluster species and their proportion during the assembly or disassembly process.Further computational studies indicate that highly charged Te(IV)ions play a key role in the stabilization of face-sharing PONbs.The photocatalytic hydrogen evolution activity of 1 has also been investigated.This work not only bridges the gap between natural and synthetic PONbs,but also deepens our understanding of the formation of facesharing octahedra.展开更多
基金The project was supported by the National Doctoral Research Foundation of China, Henan Innovation Project for University Prominent Research Talents, the Institute of Education of Henan Province and Natural Science Foundation of Henan Province
文摘A novel Ni-capped complex H4{[Ni（H2O）3]2[CeMo12O42] }· 13.5H2O has been synthesized, which is the first Silverton-type anion capped with two Ni units via three terminal oxygen atoms. Crystallographic data for the title compound： Trigonal, space group R-3, a = 13.0950（19）, b = 13.0950（19）, c = 33.029（7） A, α = β= γ = 58.727（17）A °, V = 4905.1（14） A °^3, Z = 3, Mr= 2437.17, Dc = 2.475 g/cm^3, F（000） = 3462, T = 293（2） K, μ（MoKa） = 3.564 mm^-1, Rt = 0.0369, wR2 = 0.0905 and GOF= 1.079 for 151 parameters and 1963 reflections with I 〉 2σ（I） in the range of 1.85≤θ≤25.50°.
基金supported by the National Natural Science Foundation of China(22271014,22241501,92261117,and 22101012).
文摘Polyoxometalates(POMs)are primarily constructed from{MO6}octahedra connected through corner-,edge-,and/or face-sharing modes,with face-sharing being particularly rare.Silverton clusters,characterized by their face-sharing{MO6}octahedra,have been reported for Mo and W.However,Nb-based Silverton and polyoxoniobates(PONbs)with face-sharing octahedra have not yet been synthesized,despite their occurrence in natural minerals.Herein,[(Nb_(13)O_(42)){Te_(3)(B-α-TeNb_(9)O_(33))}_(4)](1a)and its trivacant structure[(Nb_(10)O_(36)){Te_(3)(B-α-TeNb_(9)O_(33))}_(4)](2a)with the long-sought feature of face-sharing{NbO_(6)}octahedra have been synthesized for the first time.In 1a,the central{Nb_(13)O_(42)},consisting of six sets of face-sharing{Nb_(2)O_(9)}and a central Nb,is surrounded by 12 Te(IV)ions anchored on four{TeNb_(9)O_(33)}.Notably,the observed{Nb_(13)O_(42)}can be viewed as both a synthetic analogue of natural minerals and a topological isomer of the classic Silverton cluster.Moreover,small angle X-ray scattering data analysis confirms the formation of the targeted PONb cluster and determines the co-existing key cluster species and their proportion during the assembly or disassembly process.Further computational studies indicate that highly charged Te(IV)ions play a key role in the stabilization of face-sharing PONbs.The photocatalytic hydrogen evolution activity of 1 has also been investigated.This work not only bridges the gap between natural and synthetic PONbs,but also deepens our understanding of the formation of facesharing octahedra.
