Strategic Capture of the {Nb7} Polyoxometalate

Martin, Nicolas P.; Petrus, Enric; Segado, Mireia; Arteaga, Ana; Zakharov, Lev N.; Bo, Carles; Nyman, May

doi:10.1002/chem.201902770

Title: Strategic Capture of the {Nb₇} Polyoxometalate

Journal Article · 18 June 2019 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201902770 · OSTI ID:1611515

^[1];

^[2];

^[1];

^[3];

^[1]

Oregon State Univ., Corvallis, OR (United States)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
Universitat Rovira (Spain); Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)

Abstract Group V Nb‐polyoxometalate (Nb‐POM) chemistry generally lacks the elegant pH‐controlled speciation exhibited by group VI (Mo, W) POM chemistry. Here three Nb‐POM clusters were isolated and structurally characterized; [Nb ₁₄ O ₄₀ (O ₂ ) ₂ H ₃ ] ¹⁴⁻ , [((UO ₂ )(H ₂ O)) ₃ Nb ₄₆ (UO ₂ ) ₂ O ₁₃₆ H ₈ (H ₂ O) ₄ ] ²⁴⁻ , and [(Nb ₇ O ₂₂ H ₂ ) ₄ (UO ₂ ) ₇ (H ₂ O) ₆ ] ²²⁻ , that effectively capture the aqueous Nb‐POM species from pH 7 to pH 10. These Nb‐POMs illustrate a reaction pathway for control over speciation that is driven by counter‐cations (Li ⁺ ) rather than pH. The two reported heterometallic POMs (with UO ₂ ²⁺ moieties) are stabilized by replacing labile H ₂ O/HO−Nb=O with very stable O=U=O. The third isolated Nb‐POM features cis ‐yl‐oxos, prior observed only in group VI POM chemistry. Moreover, with these actinide‐heterometal contributions to the burgeoning Nb‐POM family, it now transects all major metal groups of the periodic table.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oregon State Univ., Corvallis, OR (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE

Grant/Contract Number:: SC0010802

OSTI ID:: 1611515

Alternate ID(s):: OSTI ID: 1542479

Journal Information:: Chemistry - A European Journal, Vol. 25, Issue 45; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Self-Assembly of Supramolecular Polyoxometalates: The Compact, Water-Soluble Heteropolytungstate Anion[As12IIICe16III(H2O)36W148O524]76− Wassermann, Knut; Dickman, Michael H.; Pope, Michael T. Angewandte Chemie International Edition in English, Vol. 36, Issue 1314 https://doi.org/10.1002/anie.199714451	journal	August 1997
Platinum polyoxoniobates Abramov, P. A.; Vicent, C.; Kompankov, N. B. Chemical Communications, Vol. 51, Issue 19 https://doi.org/10.1039/C5CC00315F	journal	January 2015
Reaction Dynamics of the Decaniobate Ion [HxNb10O28](6−x)− in Water Villa, Eric M.; Ohlin, C. André; Balogh, Edina Angewandte Chemie, Vol. 120, Issue 26 https://doi.org/10.1002/ange.200801125	journal	June 2008
{Nb ₂₈₈ O ₇₆₈ (OH) ₄₈ (CO ₃ ) ₁₂ }: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms Wu, Yan-Lan; Li, Xin-Xiong; Qi, Yan-Jie Angewandte Chemie, Vol. 130, Issue 28 https://doi.org/10.1002/ange.201804088	journal	June 2018
Solid-State Dynamics of Uranyl Polyoxometalates Alam, Todd M.; Liao, Zuolei; Zakharov, Lev N. Chemistry - A European Journal, Vol. 20, Issue 27 https://doi.org/10.1002/chem.201402351	journal	May 2014
A new class of soluble and stable transition-metal-substituted polyoxoniobate: [Cr2(OH)4Nb10O30]8− Son, Jung-Ho; Ohlin, C. André; Casey, William H. Dalton Transactions, Vol. 41, Issue 41 https://doi.org/10.1039/c2dt31760e	journal	January 2012
Giant Polyniobate Clusters Based on [Nb7O22]9− Units Derived from a Nb6O19 Precursor Niu, Jingyang; Ma, Pengtao; Niu, Hongyu Chemistry - A European Journal, Vol. 13, Issue 31 https://doi.org/10.1002/chem.200700612	journal	October 2007
Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites Llordés, Anna; Garcia, Guillermo; Gazquez, Jaume Nature, Vol. 500, Issue 7462 https://doi.org/10.1038/nature12398	journal	August 2013
A Chromium-Substituted Polyoxoniobate with High Ionic Conductivity Guo, Zheng-Wei; Chen, Yi; Zhao, Dan Inorganic Chemistry, Vol. 58, Issue 7 https://doi.org/10.1021/acs.inorgchem.8b03529	journal	March 2019
Evolution of Polyoxoniobate Cluster Anions Bontchev, Ranko P.; Nyman, May Angewandte Chemie, Vol. 118, Issue 40 https://doi.org/10.1002/ange.200602200	journal	October 2006
Crystal structure of the heptamolybdate( VI )(paramolybdate) ion, [Mo ₇ O ₂₄ ] ^6– , in the ammonium and potassium tetrahydrate salts Evans, Howard T.; Gatehouse, Bryan M.; Leverett, Peter J. Chem. Soc., Dalton Trans., Issue 6 https://doi.org/10.1039/DT9750000505	journal	January 1975
Co ²⁺ -Linked [NaP ₅ W ₃₀ O ₁₁₀ ] ¹⁴⁻ : A Redox-Active Metal Oxide Framework with High Electron Density Turo, Michael J.; Chen, Linfeng; Moore, Curtis E. Journal of the American Chemical Society, Vol. 141, Issue 11 https://doi.org/10.1021/jacs.9b00866	journal	March 2019
Self-Assembly and Photocatalytic Properties of Polyoxoniobates: {Nb ₂₄ O ₇₂ }, {Nb ₃₂ O ₉₆ }, and {K ₁₂ Nb ₉₆ O ₂₈₈ } Clusters Huang, Peng; Qin, Chao; Su, Zhong-Min Journal of the American Chemical Society, Vol. 134, Issue 34 https://doi.org/10.1021/ja303723u	journal	August 2012
Im Kampf gegen Krebs: Polyoxometallate als nächste Generation metallhaltiger Medikamente Bijelic, Aleksandar; Aureliano, Manuel; Rompel, Annette Angewandte Chemie, Vol. 131, Issue 10 https://doi.org/10.1002/ange.201803868	journal	October 2018
Formation of a Ring-Shaped Reduced “Metal Oxide” with the Simple Composition [(MoO3)176(H2O)80H32] Müller, Achim; Krickemeyer, Erich; Bögge, Hartmut Angewandte Chemie International Edition, Vol. 37, Issue 9 https://doi.org/10.1002/(SICI)1521-3773(19980518)37:9<1220::AID-ANIE1220>3.0.CO;2-G	journal	May 1998
Actinyl Peroxide Nanospheres Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger Angewandte Chemie, Vol. 117, Issue 14 https://doi.org/10.1002/ange.200462445	journal	March 2005
Reaction Dynamics of the Decaniobate Ion [HxNb10O28](6−x)− in Water Villa, Eric M.; Ohlin, C. André; Balogh, Edina Angewandte Chemie International Edition, Vol. 47, Issue 26 https://doi.org/10.1002/anie.200801125	journal	June 2008
The structure of the potassium isopolymolybdate K8[Mo36O12(H2O)16].nH2O (n = 36.40) Krebs, B.; Paulat-Böschen, I. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 6 https://doi.org/10.1107/S0567740882007018	journal	June 1982
Synthese und Struktur des ringförmigen, reduzierten „Metalloxids” [(MoO3)176(H2O)80H32] Müller, Achim; Krickemeyer, Erich; Bögge, Hartmut Angewandte Chemie, Vol. 110, Issue 9 https://doi.org/10.1002/(SICI)1521-3757(19980504)110:9<1278::AID-ANGE1278>3.0.CO;2-F	journal	May 1998
Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water Sures, Dylan; Segado, Mireia; Bo, Carles Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b05015	journal	July 2018
A new titanoniobate ion—completing the series [Nb10O28]6−, [TiNb9O28]7− and [Ti2Nb8O28]8− Ohlin, C. André; Villa, Eric M.; Fettinger, James C. Dalton Transactions, Issue 15 https://doi.org/10.1039/b900465c	journal	January 2009
Solid-state Structures and Solution Behavior of Alkali Salts of the $$[\hbox{Nb}_{6}\hbox{O}_{19}]^{8-}$$ Lindqvist Ion Nyman, May; Alam, Todd M.; Bonhomme, François Journal of Cluster Science, Vol. 17, Issue 2 https://doi.org/10.1007/s10876-006-0049-x	journal	March 2006
Actinyl Peroxide Nanospheres Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger Angewandte Chemie International Edition, Vol. 44, Issue 14 https://doi.org/10.1002/anie.200462445	journal	March 2005
Highly reduced and protonated aqueous solutions of [P2W18O62]6− for on-demand hydrogen generation and energy storage Chen, Jia-Jia; Symes, Mark D.; Cronin, Leroy Nature Chemistry, Vol. 10, Issue 10 https://doi.org/10.1038/s41557-018-0109-5	journal	August 2018
A luminescent polyoxoniobate lanthanide derivative {Eu ₃ (H ₂ O) ₉ [Nb ₄₈ O ₁₃₈ (H ₂ O) ₆ ]} ²⁷⁻ Chen, Shumin; Ma, Pengtao; Luo, Huihui Chemical Communications, Vol. 53, Issue 26 https://doi.org/10.1039/C7CC00591A	journal	January 2017
Molecular Growth of a Core-Shell Polyoxometalate Fang, Xikui; Kögerler, Paul; Furukawa, Yuji Angewandte Chemie International Edition, Vol. 50, Issue 22 https://doi.org/10.1002/anie.201008225	journal	April 2011
Structure, stability and photocatalytic H ₂ production by Cr-, Mn-, Fe-, Co-, and Ni-substituted decaniobate clusters Son, Jung-Ho; Wang, Jiarui; Casey, William H. Dalton Trans., Vol. 43, Issue 48 https://doi.org/10.1039/C4DT02020K	journal	January 2014
A comprehensive comparison of transition-metal and actinyl polyoxometalates Nyman, May; Burns, Peter C. Chemical Society Reviews, Vol. 41, Issue 22 https://doi.org/10.1039/c2cs35136f	journal	January 2012
Record High-Nuclearity Polyoxoniobates: Discrete Nanoclusters {Nb ₁₁₄ }, {Nb ₈₁ }, and {Nb ₅₂ }, and Extended Frameworks Based on {Cu ₃ Nb ₇₈ } and {Cu ₄ Nb ₇₈ } Jin, Lu; Zhu, Zeng-Kui; Wu, Yan-Lan Angewandte Chemie International Edition, Vol. 56, Issue 51 https://doi.org/10.1002/anie.201709565	journal	November 2017
A General Synthetic Procedure for Heteropolyniobates Nyman, M. Science, Vol. 297, Issue 5583 https://doi.org/10.1126/science.1073979	journal	August 2002
Selbstorganisation supramolekularer Polyoxometallate: [As12IIICe16III(H2O)36W148O524]76− - ein kompaktes, wasserlösliches Heteropolywolframat-Ion Wassermann, Knut; Dickman, Michael H.; Pope, Michael T. Angewandte Chemie, Vol. 109, Issue 13-14 https://doi.org/10.1002/ange.19971091311	journal	July 1997
Preparation, crystal structure, and characterization of an inorganic-organic hybrid polyoxoniobate [Cu(en)2]3[Cu(en)2(H2O)]1·5[K0·5Nb24O72H14·5]2·25H2O Wang, Jing-Ping; Niu, Hong-Yu; Niu, Jing-Yang Journal of Chemical Sciences, Vol. 120, Issue 3 https://doi.org/10.1007/s12039-008-0053-9	journal	May 2008
Chirality-Selected Chemical Modulation of Amyloid Aggregation Gao, Nan; Du, Zhi; Guan, Yijia Journal of the American Chemical Society, Vol. 141, Issue 17 https://doi.org/10.1021/jacs.8b12537	journal	April 2019
Polyoxometalate-Based Metal Organic Frameworks (POMOFs): Structural Trends, Energetics, and High Electrocatalytic Efficiency for Hydrogen Evolution Reaction Nohra, Brigitte; El Moll, Hani; Rodriguez Albelo, L. Marleny Journal of the American Chemical Society, Vol. 133, Issue 34 https://doi.org/10.1021/ja201165c	journal	August 2011
Synthesis, crystal structure and photocatalytic properties of an unprecedented arsenic-disubstituted Lindqvist-type peroxopolyoxoniobate ion: {As ₂ Nb ₄ (O ₂ ) ₄ O ₁₄ H _1.5 } ^4.5− Geng, Qiaohua; Liu, Qisen; Ma, Pengtao Dalton Trans., Vol. 43, Issue 26 https://doi.org/10.1039/C4DT00875H	journal	January 2014
{Nb ₂₈₈ O ₇₆₈ (OH) ₄₈ (CO ₃ ) ₁₂ }: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms Wu, Yan-Lan; Li, Xin-Xiong; Qi, Yan-Jie Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201804088	journal	June 2018
Assembly of a Gigantic Polyoxometalate Cluster {W ₂₀₀ Co ₈ O ₆₆₀ } in a Networked Reactor System de la Oliva, Andreu Ruiz; Sans, Victor; Miras, Haralampos N. Angewandte Chemie, Vol. 124, Issue 51 https://doi.org/10.1002/ange.201206572	journal	November 2012
Inorganic Chemistry Goes Protein Size: A Mo368 Nano-Hedgehog Initiating Nanochemistry by Symmetry Breaking Müller, Achim; Beckmann, Eike; Bögge, Hartmut Angewandte Chemie International Edition, Vol. 41, Issue 7 https://doi.org/10.1002/1521-3773(20020402)41:7<1162::AID-ANIE1162>3.0.CO;2-8	journal	April 2002
Lithium Polyniobates. A Lindqvist-Supported Lithium−Water Adamantane Cluster and Conversion of Hexaniobate to a Discrete Keggin Complex Anderson, Travis M.; Thoma, Steven G.; Bonhomme, François Crystal Growth & Design, Vol. 7, Issue 4 https://doi.org/10.1021/cg0606904	journal	April 2007
Self-Assembly of Alkali-Uranyl-Peroxide Clusters Nyman, May; Rodriguez, Mark A.; Campana, Charles F. Inorganic Chemistry, Vol. 49, Issue 17 https://doi.org/10.1021/ic1005192	journal	September 2010
Molekulares Wachstum eines Kern-Schale-Polyoxometallats Fang, Xikui; Kögerler, Paul; Furukawa, Yuji Angewandte Chemie, Vol. 123, Issue 22 https://doi.org/10.1002/ange.201008225	journal	April 2011
Acid-Stable Peroxoniobophosphate Clusters To Make Patterned Films Son, Jung-Ho; Park, Deok-Hie; Keszler, Douglas A. Chemistry - A European Journal, Vol. 21, Issue 18 https://doi.org/10.1002/chem.201500684	journal	March 2015
Evolution of Polyoxoniobate Cluster Anions Bontchev, Ranko P.; Nyman, May Angewandte Chemie International Edition, Vol. 45, Issue 40 https://doi.org/10.1002/anie.200602200	journal	October 2006
Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J. Nature Chemistry, Vol. 10, Issue 1 https://doi.org/10.1038/nchem.2874	journal	October 2017
Tetradecacobalt(II)-Containing 36-Niobate [Co ₁₄ (OH) ₁₆ (H ₂ O) ₈ Nb ₃₆ O ₁₀₆ ] ²⁰⁻ and Its Photocatalytic H ₂ Evolution Activity Niu, Jingyang; Li, Fang; Zhao, Junwei Chemistry - A European Journal, Vol. 20, Issue 32 https://doi.org/10.1002/chem.201402730	journal	July 2014
Nb ₂ O ₅ and Ta ₂ O ₅ Thin Films from Polyoxometalate Precursors: A Single Proton Makes a Difference Fullmer, Lauren B.; Mansergh, Ryan H.; Zakharov, Lev N. Crystal Growth & Design, Vol. 15, Issue 8 https://doi.org/10.1021/acs.cgd.5b00508	journal	June 2015
Sodium paradodecatungstate 20-hydrate Evans, H. T.; Rollins, O. W. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 32, Issue 5 https://doi.org/10.1107/S0567740876005827	journal	May 1976
Inorganic Chemistry Goes Protein Size: A Mo368 Nano-Hedgehog Initiating Nanochemistry by Symmetry Breaking Müller, Achim; Beckmann, Eike; Bögge, Hartmut Angewandte Chemie, Vol. 114, Issue 7 https://doi.org/10.1002/1521-3757(20020402)114:7<1210::AID-ANGE1210>3.0.CO;2-4	journal	April 2002
Rates of Oxygen Exchange between the [H _x Nb ₆ O ₁₉ ] ⁸ ^- ^x ₍ _a _q) Lindqvist Ion and Aqueous Solutions Black, Jay R.; Nyman, May; Casey, William H. Journal of the American Chemical Society, Vol. 128, Issue 45 https://doi.org/10.1021/ja065529w	journal	November 2006
Record High-Nuclearity Polyoxoniobates: Discrete Nanoclusters {Nb ₁₁₄ }, {Nb ₈₁ }, and {Nb ₅₂ }, and Extended Frameworks Based on {Cu ₃ Nb ₇₈ } and {Cu ₄ Nb ₇₈ } Jin, Lu; Zhu, Zeng-Kui; Wu, Yan-Lan Angewandte Chemie, Vol. 129, Issue 51 https://doi.org/10.1002/ange.201709565	journal	November 2017
Polyoxometalates as Potential Next-Generation Metallodrugs in the Combat Against Cancer Bijelic, Aleksandar; Aureliano, Manuel; Rompel, Annette Angewandte Chemie International Edition, Vol. 58, Issue 10 https://doi.org/10.1002/anie.201803868	journal	October 2018
Molecular growth from a Mo176 to a Mo248 cluster Müller, A.; Shah, Syed Q. N.; Bögge, H. Nature, Vol. 397, Issue 6714 https://doi.org/10.1038/16215	journal	January 1999
Assembly of a Gigantic Polyoxometalate Cluster {W ₂₀₀ Co ₈ O ₆₆₀ } in a Networked Reactor System de la Oliva, Andreu Ruiz; Sans, Victor; Miras, Haralampos N. Angewandte Chemie International Edition, Vol. 51, Issue 51 https://doi.org/10.1002/anie.201206572	journal	November 2012
Evolution of Polyoxoniobate Cluster Anions. Bontchev, Ranko P.; Nyman, May ChemInform, Vol. 37, Issue 52 https://doi.org/10.1002/chin.200652018	journal	December 2006

Cited By (2)

Capturing the Heptaniobate {Nb ₇ O ₂₂ } ⁹ ^– Anion by Covalent Bond Formation: Synthesis, Crystal Structure, and Selected Properties of {[Fe(cyclam)] ₃ Nb ₇ O ₂₂ }· ≈ 19 H ₂ O Müscher‐Polzin, Philipp; Näther, Christian; Bensch, Wolfgang Zeitschrift für anorganische und allgemeine Chemie, Vol. 646, Issue 3 https://doi.org/10.1002/zaac.201900276	journal	February 2020
Two synthetic routes generate two isopolyoxoniobates based on {Nb ₁₆ } and {Nb ₂₀ } Liang, Zhijie; Qiao, Yuanyuan; Li, Miaomiao Dalton Transactions, Vol. 48, Issue 48 https://doi.org/10.1039/c9dt04147h	journal	January 2019

Linked Research (3)

Similar Records

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Journal Article · 2021 · Angewandte Chemie · OSTI ID:1779966

Amiri, Mehran; Martin, Nicolas P.; Feng, Ching‐Lei; +2 more

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Journal Article · 2021 · Angewandte Chemie (International Edition) · OSTI ID:1786145

Amiri, Mehran; Martin, Nicolas P.; Feng, Ching‐Lei; +2 more

Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:2339563

Duan, Jiaxin Dawn; Shabbir, Hafeera; Chen, Zhihengyu; +12 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry

CSD 1919699: Experimental Crystal Structure Determination P., Martin, Nicolas; Enric, Petrus,; Mireia, Sedago, https://doi.org/10.25505/fiz.icsd.cc22flsx The current record is supplemented by this dataset	dataset	January 2019
CCDC 1919698: Experimental Crystal Structure Determination P., Martin, Nicolas; Enric, Petrus,; Mireia, Sedago, https://doi.org/10.5517/ccdc.csd.cc22flrw The current record is supplemented by this dataset	dataset	January 2019
CCDC 1919700: Experimental Crystal Structure Determination P., Martin, Nicolas; Enric, Petrus,; Mireia, Sedago, https://doi.org/10.5517/ccdc.csd.cc22flty The current record is supplemented by this dataset	dataset	January 2019

Title: Strategic Capture of the {Nb7} Polyoxometalate

Citation Formats