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学者姓名：孙燕琼
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Abstract ：
Three novel vanadoborates with crown-shaped V12B32 cluster cages were successfully synthesized, differing only in their countercation. X-ray photoelectron spectroscopy (XPS) and Bond valence sum (BVS) analyses revealed distinct V4+/V5+ ratios (11:1, 10:2, and 10:2) in the cluster cage of the three compounds. Structural analyses indicated that the valence state ratio was modulated by the countercation. The magnetic properties of these compounds were examined using variable-temperature magnetic susceptibilities and two-dimensional correlation infrared spectroscopy (2D-COS-IR) under magnetic perturbation. This approach elucidated the origin and variability of their magnetic properties, demonstrating that the vanadium valence ratio and countercation significantly influence the magnetic behaviour of vanadoborates. The present study highlights the effectiveness of the transition of the vanadium valence state in the cluster cage by altering the countercation, providing a new avenue for the study of magnetically modulated materials. © 2024 Elsevier B.V.
Keyword ：
Magnetic properties Magnetic properties Polyoxometalate Polyoxometalate Two-dimensional correlation infrared spectroscopy Cluster Two-dimensional correlation infrared spectroscopy Cluster Vanadoborate Vanadoborate
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| GB/T 7714 | Meng, M.-Z. , Shi, G.-D. , Cheng, L.-L. et al. The magnetic modulation by the valence transition of polyoxometalate [J]. | Journal of Molecular Structure , 2024 , 1318 . |
| MLA | Meng, M.-Z. et al. "The magnetic modulation by the valence transition of polyoxometalate" . | Journal of Molecular Structure 1318 (2024) . |
| APA | Meng, M.-Z. , Shi, G.-D. , Cheng, L.-L. , Chen, Y.-P. , Sun, Y.-Q. . The magnetic modulation by the valence transition of polyoxometalate . | Journal of Molecular Structure , 2024 , 1318 . |
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The first example of a Sn(IV)-containing heteropolyoxoniobate K6H18[Cu(en)2]8{[Sn(OH)2]12 (HNb7O22)8}2en88H2O (1) is built from nanoscale high-nuclearity cubic {[Sn(OH)2]12(HNb7O22)8} cluster and [Cu(en)2]2+ complexes. The cubic {[Sn(OH)2]12(HNb7O22)8} cage is composed of eight {Nb7O22} clusters and 12 SnO6 octahedrons. The eight {Nb7O22} fragments are situated at the vertices of the cubic cage, while the 12 SnO6 octahedrons are positioned along the edges of the cubic cage. The [Cu(en)2]2+ complexes link the {[Sn(OH)2]12(HNb7O22)8} clusters into two-dimensional (2D) (4,4) grid-like layers. The N-HO hydrogen bonds between the [Cu(en)2]2+ complexes and the {[Sn(OH)2]12(HNb7O22)8} clusters link the layers to form a 3D supramolecular structure. Compound 1 exhibits a good proton conductivity of 3.1 x 10-2 S cm-1 at 85 degrees C and 98% relative humidity.
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| GB/T 7714 | Wu, Ping-Xin , Lin, Yu-Jin , Sun, Yan-Qiong et al. A Two-Dimensional Layered Heteropolyoxoniobate Based on Cubic Sn(IV)-Containing {Sn12Nb56O200} Cages with Good Proton Conductivity Property [J]. | INORGANIC CHEMISTRY , 2024 , 63 (52) : 24488-24493 . |
| MLA | Wu, Ping-Xin et al. "A Two-Dimensional Layered Heteropolyoxoniobate Based on Cubic Sn(IV)-Containing {Sn12Nb56O200} Cages with Good Proton Conductivity Property" . | INORGANIC CHEMISTRY 63 . 52 (2024) : 24488-24493 . |
| APA | Wu, Ping-Xin , Lin, Yu-Jin , Sun, Yan-Qiong , Zheng, Shou-Tian . A Two-Dimensional Layered Heteropolyoxoniobate Based on Cubic Sn(IV)-Containing {Sn12Nb56O200} Cages with Good Proton Conductivity Property . | INORGANIC CHEMISTRY , 2024 , 63 (52) , 24488-24493 . |
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Atomically precise low-nuclearity (n<10) silver nanoclusters (AgNCs) have garnered significant interest due to their size-dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox-inert polyoxoniobates (PONbs) as all-inorganic ligands. This strategy not only enables the creation of novel Ag-PONb composite nanoclusters but also facilitates the synthesis of stable low-nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag-8](6+) AgNC stabilized by six highly negative [LiNb27O75](14-) polyoxoanions. This marks the first PONb-protected superatomic AgNC, designated as {Ag-8@(LiNb27O75)(6)} (Ag-8@Nb-162), with an aesthetically spherical core-shell structure. The crystalline Ag-8@Nb-162 is stable under ambient conditions, What's more, it is water-soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag-8](6+) AgNC has interesting temperature- and pH-dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti-counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb-protected AgNCs and sheds light on the development of new-type optical functional materials.
Keyword ：
fluorescence fluorescence macromolecules macromolecules nanoclusters nanoclusters polyoxoniobate polyoxoniobate silver silver
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| GB/T 7714 | Hong, Li-Hao , Yue, Sheng-Nan , Huang, Xing et al. Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster [J]. | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION , 2024 , 63 (29) . |
| MLA | Hong, Li-Hao et al. "Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster" . | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 63 . 29 (2024) . |
| APA | Hong, Li-Hao , Yue, Sheng-Nan , Huang, Xing , Sun, Cai , Cai, Ping-Wei , Sun, Yan-Qiong et al. Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster . | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION , 2024 , 63 (29) . |
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By variation of the amount of GeO2, two organic-inorganic hybrid germanoniobate frameworks with 6-connected pcu and 10-connected bct topologies were constructed from peanut-shaped {alpha-Ge12Nb38} and {beta-Ge12Nb38} clusters, respectively. The {alpha-Ge12Nb38} and {beta-Ge12Nb38} clusters contain the most Ge centers of germanoniobates reported so far. The compounds exhibit proton conduction properties with a conductivity of 3.04 x 10(-4) Scm(-3) for 1 and 1.62 x 10(-4) Scm(-3) for 2 at 85 degrees C and 98% RH. The water vapor adsorption capacities for 1 and 2 are 5.86 and 4.40 mmolg(-1), respectively.
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| GB/T 7714 | Wang, Yong-Jiang , Yu, Lan , Li, Xin-Xiong et al. Two Unprecedented Germanoniobate Frameworks Based on High-Nuclearity Peanut-Shaped {Ge12Nb38} Clusters [J]. | INORGANIC CHEMISTRY , 2024 , 63 (2) : 1388-1394 . |
| MLA | Wang, Yong-Jiang et al. "Two Unprecedented Germanoniobate Frameworks Based on High-Nuclearity Peanut-Shaped {Ge12Nb38} Clusters" . | INORGANIC CHEMISTRY 63 . 2 (2024) : 1388-1394 . |
| APA | Wang, Yong-Jiang , Yu, Lan , Li, Xin-Xiong , Sun, Yan-Qiong , Zheng, Shou-Tian . Two Unprecedented Germanoniobate Frameworks Based on High-Nuclearity Peanut-Shaped {Ge12Nb38} Clusters . | INORGANIC CHEMISTRY , 2024 , 63 (2) , 1388-1394 . |
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A 1D copper-containing organic-inorganic hybrid heteropolyoxoniobate, H3[K(H2O)6][K2(H2O)10]2[Cu(en)2(H2O)2][Cu(en)2(Nb6O19Cu(en))2]center dot 24H2O (HPONb 1), has been synthesized to heterogeneously catalyze Knoevenagel condensation at room temperature with high yields and cycling stability. The catalyst presents the best catalytic activity for Knoevenagel condensation among the polyoxometalates (POMs) reported to date. A 1D copper-containing organic-inorganic hybrid heteropolyoxoniobate catalyst for efficient catalysis of Knoevenagel condensation at room temperature.
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| GB/T 7714 | Zuo, Ya-Kun , Li, Yan-Ru , Sun, Yan-Qiong et al. Efficient catalysis of Knoevenagel condensation by 1D copper-containing heteropolyoxoniobate at room temperature [J]. | INORGANIC CHEMISTRY FRONTIERS , 2024 , 11 (7) : 1993-1997 . |
| MLA | Zuo, Ya-Kun et al. "Efficient catalysis of Knoevenagel condensation by 1D copper-containing heteropolyoxoniobate at room temperature" . | INORGANIC CHEMISTRY FRONTIERS 11 . 7 (2024) : 1993-1997 . |
| APA | Zuo, Ya-Kun , Li, Yan-Ru , Sun, Yan-Qiong , Li, Xin-Xiong , Sun, Cai , Zheng, Shou-Tian . Efficient catalysis of Knoevenagel condensation by 1D copper-containing heteropolyoxoniobate at room temperature . | INORGANIC CHEMISTRY FRONTIERS , 2024 , 11 (7) , 1993-1997 . |
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In this work, a novel organodiphosphate-containing inorganic-organic hybrid polyoxoniobate (PONb) ring {(PO3CH2CH2PO3H)(4)Nb8O16}(4-) (Nb8P8) has been achieved by a one-pot hydrothermal method. The ring is constructed from a tetragonal {Nb8O36} motif and four {PO3CH2CH2PO3H} ligands. Interestingly, Nb8P8 can be joined together via K-H2O clusters {K-2(H2O)(4)(OH)(2)} to form one-dimensional chains {[K-2(H2O)(4)(OH)(2)]Nb8P8}(n) and further linked by {Cu(en)(2)}(2+) (en = ethylenediamine) complexes, resulting in a three-dimensional supramolecular framework {[Cu(en)(2)](2)[K-2(H2O)(4)(OH)(2)]Nb8P8}3enH2O (1). 1 exhibits good chemical and thermal stability and has a high water vapor adsorption capacity of <= 224 cm(3) g(-1) (22.71 molmol(-1)) at 298 K, outperforming most of the known polyoxometalate-based materials. Impedance measurements prove that 1 can transfer protons with moderate conductivity. This study not only contributes to the structural diversity of organodiphosphate-containing PONbs and PONb rings but also provides a reference for the development of PONb-based materials with unique performance.
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| GB/T 7714 | Cong, Yu-Chen , Xiao, Hui-Ping , Cai, Ping-Wei et al. An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding [J]. | INORGANIC CHEMISTRY , 2024 , 63 (20) : 9204-9211 . |
| MLA | Cong, Yu-Chen et al. "An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding" . | INORGANIC CHEMISTRY 63 . 20 (2024) : 9204-9211 . |
| APA | Cong, Yu-Chen , Xiao, Hui-Ping , Cai, Ping-Wei , Sun, Cai , Sun, Yan-Qiong , Qi, Ming-Qiang et al. An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding . | INORGANIC CHEMISTRY , 2024 , 63 (20) , 9204-9211 . |
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An inorganic hexalanthanide-oxo-cluster-encapsulated antimotungstate, K2Na3H43[Nd6(OH)6(H2O)6(B-alpha-SbW9O33)4]2 center dot 67H2O (1), has been successfully synthesized by a facile one-step hydrothermal reaction method. The tetrahedron-shaped two-shell {Nd6(OH)6(H2O)6(B-alpha-SbW9O33)4}(1a) polyanion is composed of a novel pure lanthanide-oxo {Nd6(mu 3-OH)6(H2O)6} octahedron and {(B-alpha-SbW9O33)4} tetrahedron. After being effectively loaded onto a glassy carbon electrode (GCE) by electrostatic adsorption using polydiallyldimethyl ammonium chloride (PDDA)-functionalized multi-walled carbon nanotubes (MWCNTs), compound 1 exhibits electrochemical activity for the reduction of bromate ions with good selectivity, a high sensitivity of 186 mu A mM-1 and a detection limit that has reached 1.9 mu M. To the best of our knowledge, this is the first example of an amperometric bromate sensor based on Ln-containing antimotungstates, which will provide new materials for electrochemical sensors. An inorganic antimotungstate 1 is constructed from tetrahedron-shaped two-shell {Nd6(OH)6(H2O)6(B-alpha-SbW9O33)4} polyanions. Compound 1 exhibits electrochemical activity for the reduction of BrO3- with good selectivity, high sensitivity and low detection limit.
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| GB/T 7714 | Yu, Lan , Ye, Jing , Li, Da-Huan et al. A tetrahedron-shaped polyoxoantimotungstate encapsulating a hexanuclear octahedral lanthanide-oxo cluster for an amperometric bromate sensor [J]. | DALTON TRANSACTIONS , 2024 , 53 (11) : 5258-5265 . |
| MLA | Yu, Lan et al. "A tetrahedron-shaped polyoxoantimotungstate encapsulating a hexanuclear octahedral lanthanide-oxo cluster for an amperometric bromate sensor" . | DALTON TRANSACTIONS 53 . 11 (2024) : 5258-5265 . |
| APA | Yu, Lan , Ye, Jing , Li, Da-Huan , Sun, Yan-Qiong , Li, Xin-Xiong , Zheng, Shou-Tian . A tetrahedron-shaped polyoxoantimotungstate encapsulating a hexanuclear octahedral lanthanide-oxo cluster for an amperometric bromate sensor . | DALTON TRANSACTIONS , 2024 , 53 (11) , 5258-5265 . |
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A rare all-inorganic high-nuclearity mixed-valent {Mn11} cluster embedded polyoxoniobate, K25H43{(Te4Nb9O33)3(Nb6O19)5(TeVINb5O14)[(TeIVO3)2(MnII7MnIII4O19)]}·97H2O (1), has been synthesized by a one-pot reaction. Compound 1 contains the largest manganese cluster {Mn11} core among polyoxoniobates reported to date. {Mn11} consists of three quasi-cubane {Mn3O4} units and is simultaneously encapsulated by lacunary α-Keggin {Te4Nb9O36} and Lindqvist {Nb6O19} units. Compound 1 exhibits significant magnetic anisotropy and excellent water solubility and stability. The findings suggest a new, all-inorganic polynulear Mn-based structural paradigm for aqueous solution chemistry and magnetic materials. © 2024 The Royal Society of Chemistry.
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| GB/T 7714 | Wu, P.-X. , Chen, C.-X. , Sun, Y.-Q. et al. A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties [J]. | Chemical Communications , 2024 , 60 (67) : 8888-8891 . |
| MLA | Wu, P.-X. et al. "A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties" . | Chemical Communications 60 . 67 (2024) : 8888-8891 . |
| APA | Wu, P.-X. , Chen, C.-X. , Sun, Y.-Q. , Zheng, S.-T. . A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties . | Chemical Communications , 2024 , 60 (67) , 8888-8891 . |
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Nature seems to favor the formation of closed anion-templated silver clusters. How precisely to create non-closed sliver clusters remains an interesting challenge. In this work, we propose that the use of transition-metal-coordination-cluster substituted polyoxometalates (TMCC-substituted POMs) as templates is an effective synthetic strategy for creating the non-closed silver clusters, as demonstrated by the obtainment of four types of rare non-closed silver cluster species of Ag38-TM (TM = Co, Ni or Zn), Ag37-Zn, {Ag37-Zn}∞ and Ag36-TM (TM = Co, Ni). The idea of the strategy is to employ the TMCC-substituted POMs containing cluster modules with different bond interactions with Ag+ ions as templates to guide the formation of the non-closed silver clusters. For example, TMCC-substituted POM clusters are used as templates in this work, which contain POM modules that can coordinate with the Ag+ ions and TMCC moieties that are difficult to coordinate with the Ag+ ions, leading to the Ag+ ions being unable to form closed clusters around TMCC-substituted POM templates. The work demonstrates a promising approach to developing intriguing and unexplored non-closed silver clusters. © 2024 The Royal Society of Chemistry.
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| GB/T 7714 | Ge, R. , Cai, P.-W. , Sun, C. et al. Development of non-closed silver clusters by transition-metal-coordination-cluster substituted polyoxometalate templates [J]. | Chemical Science , 2024 , 15 (31) : 12543-12549 . |
| MLA | Ge, R. et al. "Development of non-closed silver clusters by transition-metal-coordination-cluster substituted polyoxometalate templates" . | Chemical Science 15 . 31 (2024) : 12543-12549 . |
| APA | Ge, R. , Cai, P.-W. , Sun, C. , Sun, Y.-Q. , Li, X.-X. , Zheng, S.-T. . Development of non-closed silver clusters by transition-metal-coordination-cluster substituted polyoxometalate templates . | Chemical Science , 2024 , 15 (31) , 12543-12549 . |
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Two Polyoxometalates have been constructed by simple hydrothermal synthesis using rare-earth (RE) and antimonotungstates (ATs) {B-α-SbW9O33} as raw materials with the molecular formulas of H4.5Na1.5(H2O)6(C3H5N2)3{Na(Sb3O)2[B-β-SbW8O31Dy(H2O)2]3}·12H2O (1) and H9(C3H5N2)5{[Sb6IIISbVDy2WO10(H2O)5][(B-β-SbW9O33)2(B-α-SbW9O33)]}·16H2O (2). X-ray Single crystal diffractometer analysis shows that both 1 and 2 possess trimer configurations. Polyoxoanion 1 is assembled from three trilacunary {B-β-SbW8O31Dy(H2O)2}p units linked via {Na(Sb3O)2} cluster, where the trilacunary {B-β-SbW8O31Dy(H2O)2} unit is formed by the tetralacunary {B-β-SbW8O31} unit captures one Dy(H2O)23+ cation. Polyoxoanion 2 is composed of a novel 5p−4f heterometallic cluster {Sb6IIISbVDy2WO12(H2O)5} simultaneously stabilized by two {B-β-SbW9O33} units and one {B-α-SbW9O33} unit. In addition, two-dimensional correlation infrared spectroscopy (2D COS-IR) under magnetic disturbance was measured to investigate the difference of the variable temperature magnetic susceptibility between two compounds to explore the source of magnetic properties, and further magnetic property tests indicate that 1 and 2 may exhibit single-molecule-magnet behavior with distinct frequency dependence. This work deepens the theory of 2D COS-IR and also enriches the theoretical and experimental data of magnetism. © 2024 Elsevier B.V.
Keyword ：
Hydrothermal synthesis Hydrothermal synthesis Infrared spectroscopy Infrared spectroscopy Magnetic susceptibility Magnetic susceptibility Rare earths Rare earths Single crystals Single crystals
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| GB/T 7714 | Cheng, Ling-Ling , Meng, Ming-Ze , Chen, Yi-Ping et al. Study on magnetic properties of two dysprosium(III)-substituted antimonotungstates with different substitution modes [J]. | Journal of Molecular Structure , 2024 , 1308 . |
| MLA | Cheng, Ling-Ling et al. "Study on magnetic properties of two dysprosium(III)-substituted antimonotungstates with different substitution modes" . | Journal of Molecular Structure 1308 (2024) . |
| APA | Cheng, Ling-Ling , Meng, Ming-Ze , Chen, Yi-Ping , Liu, Xin-Ting , Qiu, Zhen-Chao , Sun, Yan-Qiong . Study on magnetic properties of two dysprosium(III)-substituted antimonotungstates with different substitution modes . | Journal of Molecular Structure , 2024 , 1308 . |
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