Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL ...Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge.Herein,two enantiomeric pairs of heterometallic EuSn oxo clusters,designated as Sn_(2)EuL_(2)-R/S and Sn_(2)EuL_(4)-R/S,were strategically synthesized using axially chiral binaphthol-phosphonate ligands.These hybrid clusters exhibit dual emission,characterized by a broad ligand-derived fluorescence band superimposed with sharp,characteristic Eu^(3+)f-f transitions,which enables excitation-dependent luminescence color tuning.Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn^(4+)centers.Notably,Sn_(2)EuL_(2)-R/S demonstrates CPL activity in both near-UV(|g_(lum)|=1.7×10^(-3))and visible(|g_(lum)|=3.1×10^(-2))regions.This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.展开更多
A new metal-oxo-clusters-based inorganic framework[NaCo_(2)Mo_(2)O_(7)(OH)_(3)]_(n)(NaCoMo),named as 3D platelike ternary-oxo-cluster,has been hydrothermally synthesized and characterized by single-crystal X-ray diffr...A new metal-oxo-clusters-based inorganic framework[NaCo_(2)Mo_(2)O_(7)(OH)_(3)]_(n)(NaCoMo),named as 3D platelike ternary-oxo-cluster,has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction structure analysis,FT-IR spectroscopy,powder X-ray diffraction(PXRD),scanning electron microscope(SEM),energy-dispersive X-ray spectroscopy(EDS)analyses,X-ray photoelectron spectroscopy(XPS)and thermogravimetric analysis(TGA).Structure analysis reveals that there are no classical building units in NaCoMo,and the asymmetric units of NaCoMo are directly extended into a new platelike 3D structure.Density functional theory calculations(DFT)indicates that the crystal formation process is exothermic and the structure is extremely stable.In addition,the compound presents excellent catalytic activity in the condensation and cyclization reaction of sulfonyl hydrazides and 1,3-diketones to synthesize pyrazoles,and the yield of the desired product is up to 99%.The successful synthesis of NaCoMo represents the discovery of a new kind of non-classical polyoxometalates.展开更多
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
Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln_2O_3 as initial lanthanide materials：[Ln_4（SO_4）_4（OH）_4（H_2O）_7]·_4H_2O（Ln = Er 1,Ho 2）,and characterized by PXRD,I...Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln_2O_3 as initial lanthanide materials：[Ln_4（SO_4）_4（OH）_4（H_2O）_7]·_4H_2O（Ln = Er 1,Ho 2）,and characterized by PXRD,IR spectra,X-ray single-crystal diffraction,2D IR correlation spectra and UV-visible absorption spectra.Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural,and they are both crystallized in the orthorhombic system Pccn space group.Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er_4（μ_3-OH）_4]^8＋ cations and SO_4^2- anions.The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of（4^12.6^3）.展开更多
This study highlights the innovative use of increased rare earth elements to enhance the dielectric properties of materials and devices.The AlOC-129Ln series,features the highest number of rare earth dopants in alumin...This study highlights the innovative use of increased rare earth elements to enhance the dielectric properties of materials and devices.The AlOC-129Ln series,features the highest number of rare earth dopants in aluminum oxo clusters to date.The trivalent ions in AlOC-129Ln impart a high dipole moment,significantly elevating the dielectric constant(k)of the doped polymer films.AlOC-129Ce,in particular,exhibits the largest molecular size,which enhances interfacial effects and achieves a relative dielectric constant four times greater than that of undoped polymers and 1.5 times higher than those with single rare earth dopants.The substantial molecular size(~2.5 nm)and robust charge scattering and trapping capabilities of AlOC-129Ln reduce dielectric loss by up to 50% at high frequencies.Additionally,its excellent solution processability enhances breakdown strength by 147%,ensuring superior electrical stability.This research demonstrates the versatility of the cluster doping strategy in effectively balancing dielectric constant and loss,unveiling the promising potential of solution-processable cluster materials in electronic devices.展开更多
通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(O^(i)Pr)_(4)合成了双核钛配合物[Ti_(2)(μ_(2)-O)(Pycox)_(2)(O^(i)Pr)_(4)](1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti_(3)(μ_(2...通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(O^(i)Pr)_(4)合成了双核钛配合物[Ti_(2)(μ_(2)-O)(Pycox)_(2)(O^(i)Pr)_(4)](1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti_(3)(μ_(2)-O)_(2)(Pycox)_(2)(Ph_(2)PO_(2))_(2)(O^(i)Pr)_(4)](2)和六核钛配合物[Ti_(6)(μ_(2)-O)_(2)(μ_(3)-O)_(2)(Pycox)_(2)(Ph PO_(3))_(4)(O^(i)Pr)_(6)]·2CH_(3)CN (3)。配合物1~3的光学带隙分别为2.89、3.00和2.87 e V,其中配合物2的光电流密度可达0.1μA·cm^(-2)。展开更多
基金financially supported by the National Natural Science Foundation of China(22471268)the National Key Research and Development Project(2022YFA1503900)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1170000)the Natural Science Foundation of Fujian Province(2022J05090,2024T3003)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2022-GH03,CXZX-2024-JQ08).
文摘Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge.Herein,two enantiomeric pairs of heterometallic EuSn oxo clusters,designated as Sn_(2)EuL_(2)-R/S and Sn_(2)EuL_(4)-R/S,were strategically synthesized using axially chiral binaphthol-phosphonate ligands.These hybrid clusters exhibit dual emission,characterized by a broad ligand-derived fluorescence band superimposed with sharp,characteristic Eu^(3+)f-f transitions,which enables excitation-dependent luminescence color tuning.Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn^(4+)centers.Notably,Sn_(2)EuL_(2)-R/S demonstrates CPL activity in both near-UV(|g_(lum)|=1.7×10^(-3))and visible(|g_(lum)|=3.1×10^(-2))regions.This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.
基金financially supported by the National Natural Science Foundation of China(Nos.22001034,21871026,21804019)the Open Fund of the Jiangxi Province Key Laboratory of Synthetic Chemistry(No.JXSC202008)the Research Found of East China University of Technology(Nos.DHBK2019264,DHBK2019265,DHBK2019267)。
文摘A new metal-oxo-clusters-based inorganic framework[NaCo_(2)Mo_(2)O_(7)(OH)_(3)]_(n)(NaCoMo),named as 3D platelike ternary-oxo-cluster,has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction structure analysis,FT-IR spectroscopy,powder X-ray diffraction(PXRD),scanning electron microscope(SEM),energy-dispersive X-ray spectroscopy(EDS)analyses,X-ray photoelectron spectroscopy(XPS)and thermogravimetric analysis(TGA).Structure analysis reveals that there are no classical building units in NaCoMo,and the asymmetric units of NaCoMo are directly extended into a new platelike 3D structure.Density functional theory calculations(DFT)indicates that the crystal formation process is exothermic and the structure is extremely stable.In addition,the compound presents excellent catalytic activity in the condensation and cyclization reaction of sulfonyl hydrazides and 1,3-diketones to synthesize pyrazoles,and the yield of the desired product is up to 99%.The successful synthesis of NaCoMo represents the discovery of a new kind of non-classical polyoxometalates.
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.
基金supported by the National Natural Science Foundation of China(No.21473030)the Natural Science Foundation of Fujian Province(No.2013J01041)the Foundation of State Key Laboratory of Structural Chemistry(No.20130012)
文摘Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln_2O_3 as initial lanthanide materials：[Ln_4（SO_4）_4（OH）_4（H_2O）_7]·_4H_2O（Ln = Er 1,Ho 2）,and characterized by PXRD,IR spectra,X-ray single-crystal diffraction,2D IR correlation spectra and UV-visible absorption spectra.Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural,and they are both crystallized in the orthorhombic system Pccn space group.Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er_4（μ_3-OH）_4]^8＋ cations and SO_4^2- anions.The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of（4^12.6^3）.
基金supported by funding from the Fujian Provincial Chemistry Discipline Alliance(50025401)the National Natural Science Foundation of China(22371278)+3 种基金the National Natural Science Foundation of China(22275193,52473201)the Natural Science Foundation of Fujian Province(2021J06034)Self-deployment Project Re-search Program of Haixi Institutes,Chinese Academy of Science,CXZX-2022-GH09Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(E055AJ01,E355AJ01).
文摘This study highlights the innovative use of increased rare earth elements to enhance the dielectric properties of materials and devices.The AlOC-129Ln series,features the highest number of rare earth dopants in aluminum oxo clusters to date.The trivalent ions in AlOC-129Ln impart a high dipole moment,significantly elevating the dielectric constant(k)of the doped polymer films.AlOC-129Ce,in particular,exhibits the largest molecular size,which enhances interfacial effects and achieves a relative dielectric constant four times greater than that of undoped polymers and 1.5 times higher than those with single rare earth dopants.The substantial molecular size(~2.5 nm)and robust charge scattering and trapping capabilities of AlOC-129Ln reduce dielectric loss by up to 50% at high frequencies.Additionally,its excellent solution processability enhances breakdown strength by 147%,ensuring superior electrical stability.This research demonstrates the versatility of the cluster doping strategy in effectively balancing dielectric constant and loss,unveiling the promising potential of solution-processable cluster materials in electronic devices.
文摘通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(O^(i)Pr)_(4)合成了双核钛配合物[Ti_(2)(μ_(2)-O)(Pycox)_(2)(O^(i)Pr)_(4)](1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti_(3)(μ_(2)-O)_(2)(Pycox)_(2)(Ph_(2)PO_(2))_(2)(O^(i)Pr)_(4)](2)和六核钛配合物[Ti_(6)(μ_(2)-O)_(2)(μ_(3)-O)_(2)(Pycox)_(2)(Ph PO_(3))_(4)(O^(i)Pr)_(6)]·2CH_(3)CN (3)。配合物1~3的光学带隙分别为2.89、3.00和2.87 e V,其中配合物2的光电流密度可达0.1μA·cm^(-2)。
