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学者姓名：孙燕琼
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Abstract ：
Ln-containing polyoxoniobates (PONbs) have appealing applications in luminescence, information encryption and magnetic fields, but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln3 + ions in alkaline environments. In this paper, we are able to integrate CO3 2- and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu19 -embedded PONb H49 K16 Na13 (H2 O)63 [Eu21 O2 (OH)7 (H2 O)5 (Nb7 O22 )10 (Nb2 O6 )2 (CO3 )18 ] 91H2 O ( 1 ), which contains the highest nuclearity Eu-O clusters and the largest number of Eu3 + ions among PONbs. In addition, the film that was prepared by mixing 1 with gelatin and glycerol, exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach. This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption. (c) 2024 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Keyword ：
Acid/alkali stimulation Acid/alkali stimulation Information encryption Information encryption Lanthanide Lanthanide Luminescence Luminescence Polyoxoniobate Polyoxoniobate
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| GB/T 7714 | Xia, Wen-Jun , Wang, Yong-Jiang , Cao, Yun-Fei et al. A luminescent folded S-shaped high-nuclearity Eu19 -oxo-cluster emb e dde d polyoxoniobate for information encryption [J]. | CHINESE CHEMICAL LETTERS , 2025 , 36 (2) . |
| MLA | Xia, Wen-Jun et al. "A luminescent folded S-shaped high-nuclearity Eu19 -oxo-cluster emb e dde d polyoxoniobate for information encryption" . | CHINESE CHEMICAL LETTERS 36 . 2 (2025) . |
| APA | Xia, Wen-Jun , Wang, Yong-Jiang , Cao, Yun-Fei , Sun, Cai , Li, Xin-Xiong , Sun, Yan-Qiong et al. A luminescent folded S-shaped high-nuclearity Eu19 -oxo-cluster emb e dde d polyoxoniobate for information encryption . | CHINESE CHEMICAL LETTERS , 2025 , 36 (2) . |
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The integration of high-nuclearity lanthanide-oxo (Ln-O) clusters into polyoxotungstates (POTs) presents a formidable synthetic challenge due to intricate assembly mechanisms and the labile nature of lanthanide coordination. Herein, we present an innovative alkaline-mediated templating strategy for constructing unprecedented Ln-oxo-cluster-encapsulated POTs through the synergistic assembly of lacunary polyoxotungstate precursors with in situ generated Ln-oxo clusters. This approach employs basic N-containing ligands and selenite (SeO32-) anions as synergistic structure-directing agents. Guided by this approach, we have successfully synthesized two series of giant Ln21-oxo-cluster-embedded polyoxotungstates, H23K30(H2O)18{[Ln21(H2O)9(WO6)(SeO3)6][Ln3(SeO3)2]2(GeW10O38)9}solvent (1-Ln) (Ln = Eu, Gd, Tb, Dy) and H27Na3K21(H2O)11(MePIP)2{[Ln21(H2O)9(WO6)(SeO3)6][Ln3(SeO3)2]2(GeW10O38)9}solvent (2-Ln) (Ln = Eu, Tb, MePIP = N-methylpiperazine). Notably, these compounds feature a rare pinwheel-shaped high-nuclearity Ln21-oxo-cluster-embedded polyanion, {[Ln21(H2O)9(WO6)(SeO3)6][Ln3(SeO3)2]2(GeW10O38)9} ({Ln27Se10Ge9W91}), with a three-layered sandwich structure. Compounds 1-Eu and 2-Eu exhibit distinct proton conduction properties due to their different packing structures. In particular, 1-Eu demonstrates a high single-crystal proton conductivity of 1.8 x 10-2 S cm-1 at 98% RH and 25 degrees C along the [001] channel direction, outperforming most crystalline porous materials. Additionally, 1-Eu exhibits temperature-dependent fluorescence. The 1-Eu0.25Dy0.75 sample can emit macroscopic white light under blue irradiation. This work provides a feasible strategy for constructing high-nuclearity Ln-oxo-cluster-containing POTs and expands their application in smart proton conductive materials and multicolor luminescent systems.
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| GB/T 7714 | Cao, Yun-Fei , Jin, Xin-Rong , Xia, Wen-Jun et al. A series of pinwheel-shaped Ln21-oxo-cluster-embedded polyoxometalates as single-crystal proton-conductive and tunable photoluminescent materials [J]. | INORGANIC CHEMISTRY FRONTIERS , 2025 . |
| MLA | Cao, Yun-Fei et al. "A series of pinwheel-shaped Ln21-oxo-cluster-embedded polyoxometalates as single-crystal proton-conductive and tunable photoluminescent materials" . | INORGANIC CHEMISTRY FRONTIERS (2025) . |
| APA | Cao, Yun-Fei , Jin, Xin-Rong , Xia, Wen-Jun , Sun, Yan-Qiong , Li, Xin-Xiong , Zheng, Shou-Tian . A series of pinwheel-shaped Ln21-oxo-cluster-embedded polyoxometalates as single-crystal proton-conductive and tunable photoluminescent materials . | INORGANIC CHEMISTRY FRONTIERS , 2025 . |
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The integration of the rich electronic properties of 3d-4f heterometallic clusters with rigid and diamagnetic polyoxometalates is of great interest and is expected to yield novel materials with enhanced properties due to synergistic effects. For the first time, the study succeeds in introducing fluorescent Zn-Ln heterometallic clusters into polyoxoniobates (PONbs), forming a family of rare giant heterometallic PONbs with various architectures, including 78-metal {Zn10Eu8Nb60}, 112-metal {Zn16Ln8Nb88} (Ln = La, Y), and 165-metal {Na2Zn29Ln12Nb122} (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho). These heterometallic PONbs exhibit many appealing structural features and unique building blocks. Particularly, they are the largest 3d-4f heterometallic PONbs and also the PONbs incorporating the largest number of 3d-4f metal ions and the highest-nuclearity 3d-4f clusters known to date. Furthermore, the combination of PONbs and Zn-Ln clusters renders these new-type heterometallic PONbs multicolor luminescent characteristics and high fluorescence quantum yields, making them promising candidate cluster molecules for responsive photonic barcodes.
Keyword ：
fluorescence fluorescence high-nuclearity high-nuclearity lanthanide lanthanide polyoxometalates polyoxometalates zinc zinc
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| GB/T 7714 | Ye, Jing , Yu, Lan , Wang, Yong-Jiang et al. Giant 3d-4f Heterometallic Polyoxoniobates of {Na2Zn29Ln12Nb122}, {Zn10Eu8Nb60}, and {Zn16Ln8Nb88} with Photonic Barcodes [J]. | SMALL , 2025 . |
| MLA | Ye, Jing et al. "Giant 3d-4f Heterometallic Polyoxoniobates of {Na2Zn29Ln12Nb122}, {Zn10Eu8Nb60}, and {Zn16Ln8Nb88} with Photonic Barcodes" . | SMALL (2025) . |
| APA | Ye, Jing , Yu, Lan , Wang, Yong-Jiang , Li, Xin-Xiong , Sun, Yan-Qiong , Zheng, Shou-Tian . Giant 3d-4f Heterometallic Polyoxoniobates of {Na2Zn29Ln12Nb122}, {Zn10Eu8Nb60}, and {Zn16Ln8Nb88} with Photonic Barcodes . | SMALL , 2025 . |
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The incorporation of 3d-5p heterometallic clusters into polyoxotungstates not only enables the construction of novel and intriguing structures but also enhances the resultant materials with exceptional properties. Here, we present an unique strontium-bridged purely inorganic two-dimensional layered polyoxotungstate, H7Sr2.5(H2O)15.5[Ni7Sb6O9(OH)6(B-alpha-SiW9O34)2]& sdot;25.5H2O (1), which is composed of a sandwich-type thirteennuclear Ni-Sb heterometallic cluster {Ni7Sb6} and two {B-alpha-SiW9O34} units. Notably, compound 1 undergoes a single-crystal-to-single-crystal transformation, accompanied by the partial substitution of Sr2+ ions with Co2+ ions, resulting in a transition from a two-dimensional to a three-dimensional structure while maintaining excellent crystallinity. This process provides an opportunity to elucidate the ions exchange mechanism at the atomic level. Furthermore, electrochemical impedance studies reveal that 1 exhibits good proton conductivity, reaching 1.40 x 10-3 S cm- 1, under conditions of 85 degrees C and 98 % relative humidity.
Keyword ：
3d-5p heterometallic cluster 3d-5p heterometallic cluster Ion exchange Ion exchange Polyoxotungstates Polyoxotungstates Proton conduction Proton conduction
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| GB/T 7714 | Chen, Yi , Guo, Zheng-Wei , Li, Xin-Xiong et al. A nickel-antimony cluster-substituted polyoxotungstate-based all-inorganic two-dimensional layered material: synthesis, structure, and properties [J]. | INORGANIC CHEMISTRY COMMUNICATIONS , 2025 , 179 . |
| MLA | Chen, Yi et al. "A nickel-antimony cluster-substituted polyoxotungstate-based all-inorganic two-dimensional layered material: synthesis, structure, and properties" . | INORGANIC CHEMISTRY COMMUNICATIONS 179 (2025) . |
| APA | Chen, Yi , Guo, Zheng-Wei , Li, Xin-Xiong , Sun, Yan-Qiong , Cai, Ping-Wei , Zheng, Shou-Tian . A nickel-antimony cluster-substituted polyoxotungstate-based all-inorganic two-dimensional layered material: synthesis, structure, and properties . | INORGANIC CHEMISTRY COMMUNICATIONS , 2025 , 179 . |
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The novel Sc-containing polyoxoniobate, H16.5K9Na16.5[Sc3(Nb7O22)(Nb14O42)3]115.5H2O, has been successfully synthesized. It exhibits a unique heptameric structure and demonstrates catalytic activity towards the Knoevenagel condensation reaction, along with broad substrate compatibility.
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| GB/T 7714 | Lin, Ya-Ting , Zeng, Li , Li, Yi-Ying et al. A scandium-containing polyoxoniobate heptamer as a catalyst for the Knoevenagel condensation reaction [J]. | DALTON TRANSACTIONS , 2025 , 54 (21) : 8425-8429 . |
| MLA | Lin, Ya-Ting et al. "A scandium-containing polyoxoniobate heptamer as a catalyst for the Knoevenagel condensation reaction" . | DALTON TRANSACTIONS 54 . 21 (2025) : 8425-8429 . |
| APA | Lin, Ya-Ting , Zeng, Li , Li, Yi-Ying , Sun, Yan-Qiong , Li, Xin-Xiong , Zheng, Shou-Tian . A scandium-containing polyoxoniobate heptamer as a catalyst for the Knoevenagel condensation reaction . | DALTON TRANSACTIONS , 2025 , 54 (21) , 8425-8429 . |
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In the past, the synthesis of polyoxometalate (POM)-templated silver nanoclusters typically relied on the use of organic salts of POMs as starting templates, thereby limiting the solvent selectivity in the synthesis. The utilization of pure-inorganic POMs as starting templates in developing novel POM-templated silver nanoclusters has been neglected. Herein, we have used pure-inorganic polyoxoniobates as a starting template to synthesize a new silver nanocluster H4[Nb6O19@Ag40(iPrS)28S4] (Ag40) (iPrS = isopropylthiolate). Single-crystal X-ray diffraction analysis showed that the silver nanocluster exhibits a remarkable core-shell structure featuring a Lindqvist-type [Nb6O19]8- polyanion as a template, surrounded by 40-nucleated silver ions as the metal shell and capped by iPrS- ligands. Interestingly, the silver nanocluster exhibits significant fluorescence properties at low temperatures, demonstrating temperature-dependent fluorescence, making it a potential candidate for temperature sensing. This work provides a new strategy for new POM-templated silver nanoclusters by using pure-inorganic POMs as starting templates. It also offers new insights into the anionic template method for synthesizing silver nanoclusters.
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| GB/T 7714 | Zeng, Li , Lin, Ya-Ting , Hong, Li-Hao et al. A new silver-thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties [J]. | CRYSTENGCOMM , 2025 , 27 (18) : 2883-2887 . |
| MLA | Zeng, Li et al. "A new silver-thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties" . | CRYSTENGCOMM 27 . 18 (2025) : 2883-2887 . |
| APA | Zeng, Li , Lin, Ya-Ting , Hong, Li-Hao , Sun, Yan-Qiong , Xie, Jianping , Zheng, Shou-Tian et al. A new silver-thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties . | CRYSTENGCOMM , 2025 , 27 (18) , 2883-2887 . |
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Three novel inorganic-organic hybrid polyoxoniobates (PONbs), H27K2Na6(H2O)17[K(H2O)(Nb6O19)2(Nb6O20) (RA)2]center dot 13H2O (1, H5RA = C7H11NO7P2, risedronic acid), H21(CN3H6)12[K3(H2O)(Nb6O19)2(Nb6O20)(ZA)2]center dot 5H2O (2, H5ZA = C5H10N2O7P2, zoledronic acid, CN3H6 = guanidine) and H24(CN3H6)7K2(H2O)4[K3(H2O)2(Nb6O19)2(Nb6O20)(EA)2]center dot 8H2O (3, H5EA = C2H8O7P2, etidronic acid, CN3H6 = guanidine) were successfully synthesized. The polyoxoanion clusters are in a small boat shape and consist of {(Nb6O19)2(Nb6O20)} unit and two deprotonated RA5-, ZA5-, and EA5- ligands, respectively. Furthermore, PONb 1 can be used as an effective heterogeneous catalyst for the Knoevenagel condensation reaction with high yields and good substrate compatibility under optimal conditions. In addition, PONb 1 also has good catalytic activity in gram-scale reactions.
Keyword ：
Knoevenagel condensation reaction Knoevenagel condensation reaction Organophosphonate Organophosphonate Polyoxoniobate Polyoxoniobate
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| GB/T 7714 | Zhang, Xue-Yu , Li, Yan-Ru , Hong, Li-Hao et al. Bisphosphonate-modified boat-shaped polyoxoniobates for efficient catalysis of knoevenagel condensation [J]. | JOURNAL OF SOLID STATE CHEMISTRY , 2025 , 347 . |
| MLA | Zhang, Xue-Yu et al. "Bisphosphonate-modified boat-shaped polyoxoniobates for efficient catalysis of knoevenagel condensation" . | JOURNAL OF SOLID STATE CHEMISTRY 347 (2025) . |
| APA | Zhang, Xue-Yu , Li, Yan-Ru , Hong, Li-Hao , Wu, Ping-Xin , Cong, Yu-Chen , Mi, Ying-Hao et al. Bisphosphonate-modified boat-shaped polyoxoniobates for efficient catalysis of knoevenagel condensation . | JOURNAL OF SOLID STATE CHEMISTRY , 2025 , 347 . |
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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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A 3D tellurium-substituted heteropolyoxoniobate framework H5K3Na[Cu(en)(2)](2)[Cu(en)(0.75)(H2O)(2.5)]{[(Te2Nb19O58)(mu(3)-OH)(2)]}24H(2)O (1, en = ethylenediamine) with a 6-connected pcu topology is built from heart-shaped {Te2Nb19O60} clusters and copper complexes. The {Te2Nb19O60} cluster represents the new tellurniobate structure type with a 19-nuclearity Nb cluster. It consists of two new monovacant Lindqvist {Nb5O19} clusters, one boat-shaped {Nb9O32} cluster and two TeO32- anions. The {Te2Nb19O60} polyanions are interlinked by [Cu(en)(2)](2+) complexes into a 2D (4, 4) grid-like layer containing rhombic sheets. The Cu2+ supports the adjacent layers through Te-O-Cu-O-Te- bonds to form a three-dimensional heteropolyoxoniobate framework with 1D channels. This compound exhibits good chemical and solvent stability and proton conductivity, with a conductivity of 7.9 x 10(-3) S cm(-1) at 85 degrees C under 98% RH.
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| GB/T 7714 | Wu, Ping-Xin , Han, Yue , Lin, Yu-Jin et al. A 3D heteropolyoxoniobate framework based on heart-shaped {Te2Nb19O60} clusters with proton conductivity property [J]. | DALTON TRANSACTIONS , 2024 , 53 (17) : 7424-7429 . |
| MLA | Wu, Ping-Xin et al. "A 3D heteropolyoxoniobate framework based on heart-shaped {Te2Nb19O60} clusters with proton conductivity property" . | DALTON TRANSACTIONS 53 . 17 (2024) : 7424-7429 . |
| APA | Wu, Ping-Xin , Han, Yue , Lin, Yu-Jin , Sun, Yan-Qiong , Zheng, Shou-Tian . A 3D heteropolyoxoniobate framework based on heart-shaped {Te2Nb19O60} clusters with proton conductivity property . | DALTON TRANSACTIONS , 2024 , 53 (17) , 7424-7429 . |
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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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