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Americium Oxalate: An Experimental and Computational Investigation of Metal–Ligand Bonding

Journal Article·Wed Mar 15 00:00:00 EDT 2023· Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.2c03976·OSTI ID:1968457

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Sao Paulo (Brazil)
State Univ. of New York (SUNY), Buffalo, NY (United States)

A novel actinide-containing coordination polymer, [Am(C₂O₄)(H₂O)₃Cl] (Am-1), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional and comprised of pseudo-dimeric Am³⁺ nodes that are bridged by oxalate ligands to form sheets. Each metal center is nine-coordinate, forming a distorted capped square antiprism geometry with a C₁ symmetry, and features bound oxalate, aqua, and chloro ligands. The Am³⁺–ligand bonds were probed computationally using the quantum theory of atoms in molecules nd natural localized molecular orbital approaches to investigate the underlying mechanisms and hybrid atomic orbital contributions therein. The analyses indicate that the bonds within Am-1 are predominantly ionic and the 5f shell of the Am³⁺ metal centers does not add a significant covalent contribution to the bonds. Further, our bonding assessment is supported by measurements on the optical properties of Am-1 using diffuse reflectance and photoluminescence spectroscopies. The position of the principal absorption band at 507 nm (⁵L_6' ←⁷F_0') is notable because it is consistent with previously reported americium oxalate complexes in solution, indicating similarities in the electronic structure and ionic bonding. Compound Am-1 is an active phosphor, featuring strong bright-blue oxalate-based luminescence with no evidence of metal-centered emission.

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Similar Records / Subjects

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; São Paulo Research Foundation (FAPESP)

Grant/Contract Number:: AC05-76RL01830; SC0001136

OSTI ID:: 1968457

Report Number(s):: PNNL-SA-179534

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 62; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Curium(III) Borate Shows Coordination Environments of Both Plutonium(III) and Americium(III) Borates Polinski, Matthew J.; Wang, Shuao; Alekseev, Evgeny V. Angewandte Chemie International Edition, Vol. 51, Issue 8https://doi.org/10.1002/anie.201107956	journal	January 2012
An Americium‐Containing Metal–Organic Framework: A Platform for Studying Transplutonium Elements Ridenour, J. August; Surbella, Robert G.; Gelis, Artem V. Angewandte Chemie International Edition, Vol. 58, Issue 46https://doi.org/10.1002/anie.201909988	journal	November 2019
Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules Goodwin, Conrad A. P.; Schlimgen, Anthony W.; Albrecht‐Schönzart, Thomas E. Angewandte Chemie International Edition, Vol. 60, Issue 17https://doi.org/10.1002/anie.202017186	journal	March 2021
Concomitant Carboxylate and Oxalate Formation From the Activation of CO₂ by a Thorium(III) Complex Formanuik, Alasdair; Ortu, Fabrizio; Inman, Christopher J. Chemistry - A European Journal, Vol. 22, Issue 50https://doi.org/10.1002/chem.201604622	journal	October 2016
Nephelauxetic effect revisited: Nephelauxetic Effect Revisited Tchougréeff, Andrei L.; Dronskowski, Richard International Journal of Quantum Chemistry, Vol. 109, Issue 11https://doi.org/10.1002/qua.21989	journal	January 2009
The Chemistry of the Actinide and Transactinide Elements Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean https://doi.org/10.1007/1-4020-3598-5	book	January 2006
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
The unit cells of some americium(III)—salts with organic anions Weigel, Fritz; ter Meer, Nicolaus Inorganic and Nuclear Chemistry Letters, Vol. 3, Issue 10https://doi.org/10.1016/0020-1650(67)80094-1	journal	October 1967
Luminescence of americium (III) and europium (III) in the cubic structure ThO2 Hubert, S.; Thouvenot, P. Journal of Luminescence, Vol. 54, Issue 2https://doi.org/10.1016/0022-2313(92)90253-6	journal	September 1992
Crystal field analysis of LaCl3:Am3+ and AmCl3 and its relationship to the spectra of frozen solutions of Am3+(aquo) Carnall, W. T. Journal of the Less Common Metals, Vol. 156, Issue 1-2https://doi.org/10.1016/0022-5088(89)90421-9	journal	December 1989
Minor actinide separation in the reprocessing of spent nuclear fuels Moyer, Bruce A.; Lumetta, Gregg J.; Mincher, Bruce J. Reprocessing and Recycling of Spent Nuclear Fuelhttps://doi.org/10.1016/B978-1-78242-212-9.00011-3	book	January 2015
Luminescence study on determination of the inner-sphere hydration number of Am(III) and Nd(III) Kimura, Takaumi; Kato, Yoshiharu Journal of Alloys and Compounds, Vol. 271-273https://doi.org/10.1016/S0925-8388(98)00236-9	journal	June 1998
Actinide oxalates, solid state structures and applications Abraham, Francis; Arab-Chapelet, Bénédicte; Rivenet, Murielle Coordination Chemistry Reviews, Vol. 266-267https://doi.org/10.1016/j.ccr.2013.08.036	journal	May 2014
Interpretation of europium(III) spectra Binnemans, Koen Coordination Chemistry Reviews, Vol. 295https://doi.org/10.1016/j.ccr.2015.02.015	journal	July 2015
Organically templated Np(IV) coordination polymer with in situ formed oxalate anion (ImidazoleH)[Np(C2O4)(CH3SO3)3(H2O)2] Andreev, Grigory B.; Budantseva, Nina A.; Tananaev, Ivan G. Inorganic Chemistry Communications, Vol. 11, Issue 7https://doi.org/10.1016/j.inoche.2008.04.006	journal	July 2008
Syntheses, structures and photoluminescence of a series of lanthanide-organic frameworks involving in situ ligand formation Zhu, Xiandong; Gao, Shuiying; Li, Yafeng Journal of Solid State Chemistry, Vol. 182, Issue 3https://doi.org/10.1016/j.jssc.2008.11.012	journal	March 2009
An unprecedented two-dimensional Eu(III) coordination polymer Eu(OOC–C5H4N–CH2–CH2–COO)(OOC–COO)·2H2O formed by in situ reaction of fumaric acid and isonicotinic acid: Crystal structure and luminescent properties Ma, De-Yun; Zeng, He-Ping; Li, Ying-Wei Solid State Sciences, Vol. 11, Issue 6https://doi.org/10.1016/j.solidstatesciences.2009.02.009	journal	June 2009
Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III) Brenner, Natasha; Sperling, Joseph M.; Poe, Todd N. Inorganic Chemistry, Vol. 59, Issue 13https://doi.org/10.1021/acs.inorgchem.0c01254	journal	June 2020
Probing the Electronic Structure of a Thorium Nitride Complex by Solid-State¹⁵ N NMR Spectroscopy Sergentu, Dumitru-Claudiu; Kent, Greggory T.; Staun, Selena L. Inorganic Chemistry, Vol. 59, Issue 14https://doi.org/10.1021/acs.inorgchem.0c01263	journal	June 2020
Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”? Yu, Xiaojuan; Sergentu, Dumitru-Claudiu; Feng, Rulin Inorganic Chemistry, Vol. 60, Issue 23https://doi.org/10.1021/acs.inorgchem.1c02374	journal	November 2021
Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal–Ligand Bonding Surbella, Robert G.; Ducati, Lucas C.; Schofield, Mark H. Inorganic Chemistry, Vol. 61, Issue 45https://doi.org/10.1021/acs.inorgchem.2c02084	journal	October 2022
Coordination Modes of Americium in the Am₂ (C₂ O₄ )₃ (H₂ O)₆ ·4H₂ O Oxalate: Synthesis, Crystal Structure, Spectroscopic Characterizations and Comparison in the M₂ (C₂ O₄ )₃ (H₂ O)₆ ·n H₂ O (M = Ln, An) Series Tamain, C.; Arab-Chapelet, B.; Rivenet, M. Inorganic Chemistry, Vol. 55, Issue 1https://doi.org/10.1021/acs.inorgchem.5b01781	journal	December 2015
Crystallographic and Spectroscopic Characterization of Americium Complexes Containing the Bis[(phosphino)methyl]pyridine-1-oxide (NOPOPO) Ligand Platform Corbey, Jordan F.; Rapko, Brian M.; Wang, Zheming Inorganic Chemistry, Vol. 57, Issue 4https://doi.org/10.1021/acs.inorgchem.7b03154	journal	February 2018
Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes White, Frankie D.; Gaiser, Alyssa N.; Warzecha, Evan J. Inorganic Chemistry, Vol. 57, Issue 20https://doi.org/10.1021/acs.inorgchem.8b02085	journal	September 2018
Investigation of in Situ Oxalate Formation from 2,3-Pyrazinedicarboxylate under Hydrothermal Conditions Using Nuclear Magnetic Resonance Spectroscopy Knope, Karah E.; Kimura, Hiroshi; Yasaka, Yoshiro Inorganic Chemistry, Vol. 51, Issue 6https://doi.org/10.1021/ic3000944	journal	February 2012
Periodic Trends in Lanthanide and Actinide Phosphonates: Discontinuity between Plutonium and Americium Diwu, Juan; Grant, Daniel J.; Wang, Shuao Inorganic Chemistry, Vol. 51, Issue 12https://doi.org/10.1021/ic300742p	journal	June 2012
Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV (^Ar acnac)₄ Complexes (An = Th, U, Np, Pu;^Ar acnac = ArN C(Ph)CHC(Ph)O ; Ar = 3,5-^t Bu₂ C₆ H₃ ) Schnaars, David D.; Gaunt, Andrew J.; Hayton, Trevor W. Inorganic Chemistry, Vol. 51, Issue 15https://doi.org/10.1021/ic301109f	journal	July 2012
Gadolinium Oxalate Derivatives with Enhanced Magnetocaloric Effect via Ionothermal Synthesis Meng, Yan; Chen, Yan-Cong; Zhang, Ze-Min Inorganic Chemistry, Vol. 53, Issue 17https://doi.org/10.1021/ic501013x	journal	August 2014
Hydrothermal Synthesis of a Novel Uranium Oxalate/Glycolate via In-Situ Ligand Formation Knope, Karah E.; Cahill, Christopher L. Inorganic Chemistry, Vol. 46, Issue 16https://doi.org/10.1021/ic700700e	journal	August 2007
Directed Synthesis of Crystalline Plutonium(III) and (IV) Oxalates: Accessing Redox-Controlled Separations in Acidic Solutions Runde, Wolfgang; Brodnax, Lia F.; Goff, George Inorganic Chemistry, Vol. 48, Issue 13https://doi.org/10.1021/ic900344u	journal	July 2009
Periodic Trends in Actinide Phosphonates: Divergence and Convergence between Thorium, Uranium, Neptunium, and Plutonium Systems Nelson, Anna-Gay D.; Bray, Travis H.; Stanley, Forrest A. Inorganic Chemistry, Vol. 48, Issue 10https://doi.org/10.1021/ic900484w	journal	May 2009
Intramolecular energy transfer and sensitized luminescence in actinide(III) β-diketone chelates Nugent, Leonard J.; Burnett, J. L.; Baybarz, R. D. The Journal of Physical Chemistry, Vol. 73, Issue 5https://doi.org/10.1021/j100725a060	journal	May 1969
van der Waals Volumes and Radii Bondi, A. The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451https://doi.org/10.1021/j100785a001	journal	March 1964
Differentiating between Trivalent Lanthanides and Actinides Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao Journal of the American Chemical Society, Vol. 134, Issue 25https://doi.org/10.1021/ja303804r	journal	June 2012
Covalency in Americium(III) Hexachloride Cross, Justin N.; Su, Jing; Batista, Enrique R. Journal of the American Chemical Society, Vol. 139, Issue 25https://doi.org/10.1021/jacs.7b03755	journal	June 2017
Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly Surbella, Robert G.; Ducati, Lucas C.; Pellegrini, Kristi L. Journal of the American Chemical Society, Vol. 139, Issue 31https://doi.org/10.1021/jacs.7b05689	journal	July 2017
Uncovering the Origin of Divergence in the CsM(CrO₄ )₂ (M = La, Pr, Nd, Sm, Eu; Am) Family through Examination of the Chemical Bonding in a Molecular Cluster and by Band Structure Analysis Galley, Shane S.; Arico, Alexandra A.; Lee, Tsung-Han Journal of the American Chemical Society, Vol. 140, Issue 5https://doi.org/10.1021/jacs.7b09474	journal	January 2018
Emergence of californium as the second transitional element in the actinide series Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E. Nature Communications, Vol. 6, Issue 1https://doi.org/10.1038/ncomms7827	journal	April 2015
Syntheses, structures and luminescence properties of cadmium(II) coordination polymers with in situ formed oxalate and bis(chelating) bridging ligands Zhang, Jian-Yong; Yue, Qi; Jia, Qin-Xiang CrystEngComm, Vol. 10, Issue 10https://doi.org/10.1039/B807165A	journal	January 2008
Hirshfeld surface analysis Spackman, Mark A.; Jayatilaka, Dylan CrystEngComm, Vol. 11, Issue 1https://doi.org/10.1039/B818330A	journal	January 2009
In situ 2,5-pyrazinedicarboxylate and oxalate ligands synthesis leading to a microporous europium–organic framework capable of selective sensing of small molecules Ma, Deyun; Wang, Weixia; Li, Yingwei CrystEngComm, Vol. 12, Issue 12https://doi.org/10.1039/C0CE00135J	journal	January 2010
Two-/three-dimensional open lanthanide–organic frameworks containing rigid/flexible dicarboxylate ligands: synthesis, crystal structure and photoluminescent properties Wang, Ping; Fan, Rui-Qing; Liu, Xin-Rong CrystEngComm, Vol. 15, Issue 10https://doi.org/10.1039/C3CE26684B	journal	January 2013
Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions Sturzbecher-Hoehne, M.; Yang, P.; D'Aléo, A. Dalton Transactions, Vol. 45, Issue 24https://doi.org/10.1039/C6DT00328A	journal	January 2016
A new Pu( iii ) coordination geometry in (C₅ H₅ NBr)₂ [PuCl₃ (H₂ O)₅ ]·2Cl·2H₂ O as obtained via supramolecular assembly in aqueous, high chloride media Surbella, Robert G.; Ducati, Lucas C.; Pellegrini, Kristi L. Chemical Communications, Vol. 53, Issue 78https://doi.org/10.1039/C7CC05988D	journal	January 2017
Plutonium chlorido nitrato complexes: ligand competition and computational metrics for assembly and bonding Surbella, Robert G.; Ducati, Lucas C.; Autschbach, Jochen Chemical Communications, Vol. 54, Issue 85https://doi.org/10.1039/C8CC05578E	journal	January 2018
A series of dithiocarbamates for americium, curium, and californium Cary, Samantha K.; Su, Jing; Galley, Shane S. Dalton Transactions, Vol. 47, Issue 41https://doi.org/10.1039/C8DT02658K	journal	January 2018
Spectroscopic speciation of aqueous Am( iii )–oxalate complexes Kim, H. -K.; Jeong, K.; Cho, H. -R. Dalton Transactions, Vol. 48, Issue 27https://doi.org/10.1039/C9DT01087D	journal	January 2019
Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes Windorff, Cory J.; Celis-Barros, Cristian; Sperling, Joseph M. Chemical Science, Vol. 11, Issue 10https://doi.org/10.1039/C9SC05268B	journal	January 2020
Beyond structural motifs: the frontier of actinide-containing metal–organic frameworks Martin, Corey R.; Leith, Gabrielle A.; Shustova, Natalia B. Chemical Science, Vol. 12, Issue 21https://doi.org/10.1039/D1SC01827B	journal	January 2021
Absorption Spectrum of Americium Tricyclopentadienide Pappalardo, R.; Carnall, W. T.; Fields, P. R. The Journal of Chemical Physics, Vol. 51, Issue 2https://doi.org/10.1063/1.1672081	journal	July 1969
Low‐Temperature Optical Absorption of Americium Halides Pappalardo, R. G.; Carnall, W. T.; Fields, P. R. The Journal of Chemical Physics, Vol. 51, Issue 3https://doi.org/10.1063/1.1672121	journal	August 1969
The Solution Absorption Spectra of Americium(III), (V), and (VI) Stephanou, S. E.; Nigon, J. P.; Penneman, R. A. The Journal of Chemical Physics, Vol. 21, Issue 1https://doi.org/10.1063/1.1698619	journal	January 1953
Measurement of local magnetic fields in actinide tetrafluorides Walter, Eric D.; Capan, Cigdem; Casella, Amanda J. The Journal of Chemical Physics, Vol. 154, Issue 21https://doi.org/10.1063/5.0052323	journal	June 2021
Review: Solvent Systems Combining Neutral and Acidic Extractants for Separating Trivalent Lanthanides from the Transuranic Elements Lumetta, Gregg J.; Gelis, Artem V.; Vandegrift, George F. Solvent Extraction and Ion Exchange, Vol. 28, Issue 3https://doi.org/10.1080/07366291003684253	journal	April 2010
Structure of lanthanum chloride oxalate trihydrate Baker, P.; Smith, A. J. Acta Crystallographica Section C Crystal Structure Communications, Vol. 46, Issue 6https://doi.org/10.1107/S0108270189009248	journal	June 1990
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767https://doi.org/10.1107/S0567739476001551	journal	September 1976
Optical Absorption Characteristics For 7F0'→5L6' and 7F0'→ 7F6' Transitions of Trivalent Americium Ion in Aqueous Electrolyte Mixtures Zalupski, Peter R.; Grimes, Travis S.; Heathman, Colt R. Applied Spectroscopy, Vol. 71, Issue 12https://doi.org/10.1177/0003702817721528	journal	July 2017
Nephelauxetic Effect and Hypersensitivity in the Optical Spectra of Actinides Barbanel’, A. ract, Vol. 78, Issue s1https://doi.org/10.1524/ract.1997.78.special-issue.91	journal	December 1997
Luminescence study on solvation of americium(III), curium(III) and several lanthanide(III) ions in nonaqueous and binary mixed solvents Kimura, T.; Nagaishi, R.; Kato, Y. Radiochimica Acta, Vol. 89, Issue 3https://doi.org/10.1524/ract.2001.89.3.125	journal	January 2001