Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mech...Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mechanism and precisely controlling their properties.However,owing to considerable synthetic difficulties,achieving this goal remains a formidable challenge.Herein,we report the synthesis of two novel high-nuclearity ZrOCs,namely[Zr_(16)(μ_(3)-O/OH)_(24)(μ_(2)-OH)_(4)(QE)_(4)(PA)_(20)](Zr_(16);H_(2)QE=2,8-quinolinediol;HPA=propanoic acid)and[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(PA)_(20)](Zr20),via a facile solvent-induced synthetic strategy.Surprisingly,we found that Zr16 and Zr20 exhibit a“mother-daughter”relationship,where Zr16,as the“daughter”,is embedded within Zr20,the“mother”,with the PA ligands excluded.Moreover,Zr20 can react with benzoic acid(HBA)via post-synthetic reactions to yield another new cluster,[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(BA)_(20)](Zr20-BA),which retains the metal core and QE ligands of Zr20,with only the peripheral PA ligands replaced by BA ligands,highlighting the framework stability and flexibility of ligand shell of Zr20.Of note,Zr20 exhibited better thermal catalytic cycloaddition of CO_(2)and epoxides performance due to the rich Lewis acidity of Zr sites,achieving near-complete conversion of diverse epoxides.This work not only expands the structural landscape of high-nuclearity Zr OCs but also provides deeper insights into their underlying assembly mechanism.展开更多
A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw mate...A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to mono-clinic P21/n space group, a= 1.2952(2), b = 1.6659(10), c= 1.3956(12) nm, β=106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (/>2σ(/)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octa-hedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MovI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.展开更多
The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compou...The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857（3）, b = 12.9619（18）, c = 20.204（3） A, β = 105.692（2）°, V= 6015.0（14） A3, Z = 4, Dc= 2.473 g/cm^3, M,.= 2239.68, F（000） = 4432, R = 0.0725, wR = 0.1524 and GOOF= 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO4^3- vip.展开更多
基金supported by the National Natural Science Foundation of China(22325105,22201159,22171164,91961105,92361301,52261135637)the Natural Science Foundation of Shandong Province(ZR2021QB077,ZR2024MB120)the Doctoral Program of Liaocheng University(318051944)。
文摘Synthesizing zirconium-oxo clusters(ZrOCs)with precisely defined“mother-daughter”architectures(large clusters containing smaller cluster units)is essential for gaining a profound understanding of their assembly mechanism and precisely controlling their properties.However,owing to considerable synthetic difficulties,achieving this goal remains a formidable challenge.Herein,we report the synthesis of two novel high-nuclearity ZrOCs,namely[Zr_(16)(μ_(3)-O/OH)_(24)(μ_(2)-OH)_(4)(QE)_(4)(PA)_(20)](Zr_(16);H_(2)QE=2,8-quinolinediol;HPA=propanoic acid)and[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(PA)_(20)](Zr20),via a facile solvent-induced synthetic strategy.Surprisingly,we found that Zr16 and Zr20 exhibit a“mother-daughter”relationship,where Zr16,as the“daughter”,is embedded within Zr20,the“mother”,with the PA ligands excluded.Moreover,Zr20 can react with benzoic acid(HBA)via post-synthetic reactions to yield another new cluster,[Zr_(20)(μ_(3)-O/OH)_(32)(μ_(2)-OH)_(4)(QE)_(8)(BA)_(20)](Zr20-BA),which retains the metal core and QE ligands of Zr20,with only the peripheral PA ligands replaced by BA ligands,highlighting the framework stability and flexibility of ligand shell of Zr20.Of note,Zr20 exhibited better thermal catalytic cycloaddition of CO_(2)and epoxides performance due to the rich Lewis acidity of Zr sites,achieving near-complete conversion of diverse epoxides.This work not only expands the structural landscape of high-nuclearity Zr OCs but also provides deeper insights into their underlying assembly mechanism.
文摘A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to mono-clinic P21/n space group, a= 1.2952(2), b = 1.6659(10), c= 1.3956(12) nm, β=106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (/>2σ(/)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octa-hedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MovI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.
基金This work was supported by the Science and Technology Development Foundation of Fuzhou University (No.2004-xq-05)the Scientific Research Foundation of Fujian Provincial Education Department (No. JB04010)
文摘The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857（3）, b = 12.9619（18）, c = 20.204（3） A, β = 105.692（2）°, V= 6015.0（14） A3, Z = 4, Dc= 2.473 g/cm^3, M,.= 2239.68, F（000） = 4432, R = 0.0725, wR = 0.1524 and GOOF= 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO4^3- vip.
