Near-infrared C-term MCD spectroscopy of octahedral uranium (V) complexes
Abstract
C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d–d and f–f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(V) complexes of Oh symmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study, C-term NIR MCD of the Laporte forbidden f–f transitions of [UCl6]- and [UF6]- are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ7 → Γ8 transitions in [UF6]-. The experimental NIR MCD studies were further extended to [U(OC6F5)6]-, [U(CH2SiMe3)6]-, and [U(NC(tBu)(Ph))6]- to evaluate the effects of ligand-type on the f–f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f–f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(V) hexahalide complexes, via the inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(V) complexes and identify areas for continued theoretical development.
- Authors:
-
[2];
[1];
[3];
[4];
[2];
[1]
- Univ. of Rochester, NY (United States)
- State Univ. of New York at Buffalo, NY (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC). Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1874921
- Alternate Identifier(s):
- OSTI ID: 1773551
- Report Number(s):
- LA-UR-21-21245
Journal ID: ISSN 1477-9226; TRN: US2307158
- Grant/Contract Number:
- 89233218CNA000001; SC0016002; SC0001136; AC02-05CH11231; 2020LANLE372
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 16; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Curran, Daniel J., Ganguly, Gaurab, Heit, Yonaton N., Wolford, Nikki J., Minasian, Stefan G., Löble, Matthias W., Cary, Samantha K., Kozimor, Stosh A., Autschbach, Jochen, and Neidig, Michael L. Near-infrared C-term MCD spectroscopy of octahedral uranium (V) complexes. United States: N. p., 2021.
Web. doi:10.1039/d1dt00513h.
Curran, Daniel J., Ganguly, Gaurab, Heit, Yonaton N., Wolford, Nikki J., Minasian, Stefan G., Löble, Matthias W., Cary, Samantha K., Kozimor, Stosh A., Autschbach, Jochen, & Neidig, Michael L. Near-infrared C-term MCD spectroscopy of octahedral uranium (V) complexes. United States. https://doi.org/10.1039/d1dt00513h
Curran, Daniel J., Ganguly, Gaurab, Heit, Yonaton N., Wolford, Nikki J., Minasian, Stefan G., Löble, Matthias W., Cary, Samantha K., Kozimor, Stosh A., Autschbach, Jochen, and Neidig, Michael L. Thu .
"Near-infrared C-term MCD spectroscopy of octahedral uranium (V) complexes". United States. https://doi.org/10.1039/d1dt00513h. https://www.osti.gov/servlets/purl/1874921.
@article{osti_1874921,
title = {Near-infrared C-term MCD spectroscopy of octahedral uranium (V) complexes},
author = {Curran, Daniel J. and Ganguly, Gaurab and Heit, Yonaton N. and Wolford, Nikki J. and Minasian, Stefan G. and Löble, Matthias W. and Cary, Samantha K. and Kozimor, Stosh A. and Autschbach, Jochen and Neidig, Michael L.},
abstractNote = {C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d–d and f–f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(V) complexes of Oh symmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study, C-term NIR MCD of the Laporte forbidden f–f transitions of [UCl6]- and [UF6]- are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ7 → Γ8 transitions in [UF6]-. The experimental NIR MCD studies were further extended to [U(OC6F5)6]-, [U(CH2SiMe3)6]-, and [U(NC(tBu)(Ph))6]- to evaluate the effects of ligand-type on the f–f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f–f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(V) hexahalide complexes, via the inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(V) complexes and identify areas for continued theoretical development.},
doi = {10.1039/d1dt00513h},
journal = {Dalton Transactions},
number = 16,
volume = 50,
place = {United States},
year = {Thu Apr 01 00:00:00 EDT 2021},
month = {Thu Apr 01 00:00:00 EDT 2021}
}
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Works referenced in this record:
Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex
journal, February 2012
- Seaman, Lani A.; Wu, Guang; Edelstein, Norman
- Journal of the American Chemical Society, Vol. 134, Issue 10
Experimental and Computational Studies of a Uranium Metallacyclocumulene
journal, February 2017
- Zhang, Lei; Fang, Bo; Hou, Guohua
- Organometallics, Vol. 36, Issue 4
On the site symmetry of uranyl crown compounds in solution
journal, February 2003
- De Houwer, Sandy; Servaes, Kelly; Görller-Walrand, Christiane
- Physical Chemistry Chemical Physics, Vol. 5, Issue 6
Spectroscopic Determination of the Electronic Structure of a Uranium Single-Ion Magnet
journal, January 2019
- Coutinho, Joana T.; Perfetti, Mauro; Baldoví, José J.
- Chemistry - A European Journal, Vol. 25, Issue 7
Covalency effects on the ligand field splittings of octahedral 5f7 compounds
journal, March 1974
- Edelstein, N.; Brown, D.; Whittaker, B.
- Inorganic Chemistry, Vol. 13, Issue 3
Siloxides as Supporting Ligands in Uranium(III)-Mediated Small-Molecule Activation
journal, November 2012
- Mougel, Victor; Camp, Clément; Pécaut, Jacques
- Angewandte Chemie International Edition, Vol. 51, Issue 49
Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study
journal, November 2015
- Beekmeyer, Reece; Kerridge, Andrew
- Inorganics, Vol. 3, Issue 4
Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
journal, December 2016
- Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio
- Nature Chemistry, Vol. 9, Issue 6
Investigation of the Electronic Structure of Mono(1,1′-Diamidoferrocene) Uranium(IV) Complexes
journal, August 2013
- Duhović, Selma; Oria, Jeremy V.; Odoh, Samuel O.
- Organometallics, Vol. 32, Issue 20
Investigation of the Electronic Ground States for a Reduced Pyridine(diimine) Uranium Series: Evidence for a Ligand Tetraanion Stabilized by a Uranium Dimer
journal, April 2015
- Anderson, Nickolas H.; Odoh, Samuel O.; Williams, Ursula J.
- Journal of the American Chemical Society, Vol. 137, Issue 14
Ab Initio Study of Covalency in the Ground versus Core-Excited States and X-ray Absorption Spectra of Actinide Complexes
journal, September 2018
- Sergentu, Dumitru-Claudiu; Duignan, Thomas J.; Autschbach, Jochen
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
High energy resolution x-ray absorption spectroscopy study of uranium in varying valence states
journal, December 2010
- Vitova, T.; Kvashnina, K. O.; Nocton, G.
- Physical Review B, Vol. 82, Issue 23
A Combined Mössbauer, Magnetic Circular Dichroism, and Density Functional Theory Approach for Iron Cross-Coupling Catalysis: Electronic Structure, In Situ Formation, and Reactivity of Iron-Mesityl-Bisphosphines
journal, June 2014
- Daifuku, Stephanie L.; Al-Afyouni, Malik H.; Snyder, Benjamin E. R.
- Journal of the American Chemical Society, Vol. 136, Issue 25
Modern quantum chemistry with [Open]Molcas
journal, June 2020
- Aquilante, Francesco; Autschbach, Jochen; Baiardi, Alberto
- The Journal of Chemical Physics, Vol. 152, Issue 21
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl 6 2– (M = Ti, Zr, Hf, U) and UOCl 5 – Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
journal, March 2012
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 134, Issue 12
Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides
journal, October 2015
- Prieur, D.; Lebreton, F.; Martin, P. M.
- Journal of Solid State Chemistry, Vol. 230
Bonding in tris(.eta.5-cyclopentadienyl) actinide complexes. 2. The ground electronic configurations of "base-free" Cp3An complexes (An = thorium, protactinium, uranium, neptunium, plutonium)
journal, April 1989
- Bursten, Bruce E.; Rhodes, Larry F.; Strittmatter, Richard J.
- Journal of the American Chemical Society, Vol. 111, Issue 8
Small Molecule Activation by Uranium Tris(aryloxides): Experimental and Computational Studies of Binding of N 2 , Coupling of CO, and Deoxygenation Insertion of CO 2 under Ambient Conditions
journal, June 2011
- Mansell, Stephen M.; Kaltsoyannis, Nikolas; Arnold, Polly L.
- Journal of the American Chemical Society, Vol. 133, Issue 23
Molecular and Electronic Structure of Dinuclear Uranium Bis-μ-Oxo Complexes with Diamond Core Structural Motifs
journal, July 2014
- Schmidt, Anna-Corina; Heinemann, Frank W.; Lukens, Wayne W.
- Journal of the American Chemical Society, Vol. 136, Issue 34
The electronic structure of organometallic complexes of the f elements.XXI. The crystal field splitting pattern of perdeuterated tris(η5-cyclopentadienyl)-uranium(IV)chloride in the low energy range
journal, December 1987
- Amberger, Hanns-Dieter; Reddmann, Hauke; Edelstein, Norman M.
- Inorganica Chimica Acta, Vol. 139, Issue 1-2
Ligand effects on electronic structure and bonding in U( iii ) coordination complexes: a combined MCD, EPR and computational study
journal, January 2020
- Wolford, Nikki J.; Yu, Xiaojuan; Bart, Suzanne C.
- Dalton Transactions, Vol. 49, Issue 41
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ Backbonding
journal, May 2014
- La Pierre, Henry S.; Scheurer, Andreas; Heinemann, Frank W.
- Angewandte Chemie International Edition, Vol. 53, Issue 28
Multiple-Bond Metathesis Mediated by Sterically Pressured Uranium Complexes
journal, April 2006
- Castro-Rodríguez, Ingrid; Nakai, Hidetaka; Meyer, Karsten
- Angewandte Chemie International Edition, Vol. 45, Issue 15
Use of 77 Se and 125 Te NMR Spectroscopy to Probe Covalency of the Actinide-Chalcogen Bonding in [Th(E n ){N(SiMe 3 ) 2 } 3 ] − (E = Se, Te; n = 1, 2) and Their Oxo-Uranium(VI) Congeners
journal, January 2016
- Smiles, Danil E.; Wu, Guang; Hrobárik, Peter
- Journal of the American Chemical Society, Vol. 138, Issue 3
Synthesis and Redox Chemistry of High-Valent Uranium Aryloxides
journal, April 2009
- Fortier, Skye; Wu, Guang; Hayton, Trevor W.
- Inorganic Chemistry, Vol. 48, Issue 7
Theoretical insight into the magnetic circular dichroism of uranium N 6,7 ‐edge X‐ray absorption
journal, October 2019
- Ramanantoanina, Harry; Gruden, Maja
- International Journal of Quantum Chemistry, Vol. 120, Issue 3
Tailoring the Electronic Structure of Uranium Mono(imido) Species through Ligand Variation
journal, February 2018
- Kiernicki, John J.; Tatebe, Caleb J.; Zeller, Matthias
- Inorganic Chemistry, Vol. 57, Issue 4
Synthesis and Characterization of N-Heterocyclic Carbene Complexes of Uranium(III)
journal, February 2004
- Nakai, Hidetaka; Hu, Xile; Zakharov, Lev N.
- Inorganic Chemistry, Vol. 43, Issue 3
Mapping the Electronic Structure of the Uranium(VI) Dinitride Molecule, UN 2
journal, July 2020
- Liu, Gaoxiang; Zhang, Chaoqun; Ciborowski, Sandra M.
- The Journal of Physical Chemistry A, Vol. 124, Issue 32
Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands
journal, July 2013
- Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola
- Journal of the American Chemical Society, Vol. 135, Issue 29
Magnetic circular dichroism of UCl 6 − in the ligand-to-metal charge-transfer spectral region
journal, January 2017
- Gendron, Frédéric; Fleischauer, Valerie E.; Duignan, Thomas J.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 26
Theory of vibronic intensity borrowing. Comparison of Herzberg‐Teller and Born‐Oppenheimer coupling
journal, May 1973
- Orlandi, G.; Siebrand, W.
- The Journal of Chemical Physics, Vol. 58, Issue 10
Probing the Chemistry, Electronic Structure and Redox Energetics in Organometallic Pentavalent Uranium Complexes
journal, December 2008
- Graves, Christopher R.; Vaughn, Anthony E.; Schelter, Eric J.
- Inorganic Chemistry, Vol. 47, Issue 24
Bonding in Uranium(V) Hexafluoride Based on the Experimental Electron Density Distribution Measured at 20 K
journal, February 2017
- Gianopoulos, Christopher G.; Zhurov, Vladimir V.; Minasian, Stefan G.
- Inorganic Chemistry, Vol. 56, Issue 4
Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States
journal, November 2019
- Ganguly, Gaurab; Sergentu, Dumitru‐Claudiu; Autschbach, Jochen
- Chemistry – A European Journal, Vol. 26, Issue 8
Ab Initio Study of Vibronic and Magnetic 5f-to-5f and Dipole-Allowed 5f-to-6d and Charge-Transfer Transitions in [UX 6 ] n − (X = Cl, Br; n = 1, 2)
journal, June 2020
- Ganguly, Gaurab; Ludowieg, Herbert D.; Autschbach, Jochen
- Journal of Chemical Theory and Computation, Vol. 16, Issue 8
Bio-inspired nano-traps for uranium extraction from seawater and recovery from nuclear waste
journal, April 2018
- Sun, Qi; Aguila, Briana; Perman, Jason
- Nature Communications, Vol. 9, Issue 1
Similar ligand–metal bonding for transition metals and actinides? 5f 1 U(C 7 H 7 ) 2 − versus 3d n metallocenes
journal, January 2018
- Sergentu, Dumitru-Claudiu; Gendron, Frédéric; Autschbach, Jochen
- Chemical Science, Vol. 9, Issue 29
Examining the Effects of Ligand Variation on the Electronic Structure of Uranium Bis(imido) Species
journal, October 2016
- Kiernicki, John J.; Ferrier, Maryline G.; Lezama Pacheco, Juan S.
- Journal of the American Chemical Society, Vol. 138, Issue 42
Electron paramagnetic resonance and optical studies of pentavalent uranium
journal, July 1973
- Lewis, W. Burton; Hecht, Harry G.; Eastman, Michael P.
- Inorganic Chemistry, Vol. 12, Issue 7
Analysis of the Absorption Spectrum of Cesium Uranium (V) Hexafluoride
journal, January 1965
- Reisfeld, Martin J.; Crosby, Glenn A.
- Inorganic Chemistry, Vol. 4, Issue 1
Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review
journal, July 2013
- Aminov, L. K.; Kurkin, I. N.; Malkin, B. Z.
- Physics of the Solid State, Vol. 55, Issue 7
High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds
journal, July 2016
- Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 29
Synchrotron applications to f-element research in the nuclear fuel cycle
journal, January 2015
- Denecke, Melissa A.
- Dalton Transactions, Vol. 44, Issue 6
OpenMolcas: From Source Code to Insight
journal, September 2019
- Fdez. Galván, Ignacio; Vacher, Morgane; Alavi, Ali
- Journal of Chemical Theory and Computation, Vol. 15, Issue 11
Pentavalent uranium trans-dihalides and -pseudohalides
journal, January 2012
- Lewis, Andrew J.; Nakamaru-Ogiso, Eiko; Kikkawa, James M.
- Chemical Communications, Vol. 48, Issue 41
EPR studies of some f n and d n electronic impurities in KTaO 3 single crystals
journal, September 1984
- Abraham, M. M.; Boatner, L. A.; Olson, D. N.
- The Journal of Chemical Physics, Vol. 81, Issue 6
Characteristics of chemical bonding of pentavalent uranium in La-doped UO 2
journal, January 2017
- Butorin, Sergei M.; Kvashnina, Kristina O.; Prieur, Damien
- Chemical Communications, Vol. 53, Issue 1
Structures of chloro-uranium species in molten LiCl–BeCl2 eutectic: A combined X-ray and electronic absorption spectroscopy study
journal, September 2005
- Volkovich, V. A.; May, I.; Griffiths, T. R.
- Journal of Nuclear Materials, Vol. 344, Issue 1-3
Calculation of Dipole-Forbidden 5f Absorption Spectra of Uranium(V) Hexa-Halide Complexes
journal, February 2018
- Heit, Yonaton N.; Gendron, Frédéric; Autschbach, Jochen
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 4
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory
journal, January 2014
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Chem. Sci., Vol. 5, Issue 1
Crystallographic and spectroscopic characterization and reactivities of a mononuclear non-haem iron(III)-superoxo complex
journal, December 2014
- Hong, Seungwoo; Sutherlin, Kyle D.; Park, Jiyoung
- Nature Communications, Vol. 5, Issue 1
Optically Active Vibrations of Cesium Actinide(V) Hexafluorides (CsUF 6 , CsNpF 6 , and CsPuF 6 )
journal, June 1990
- Ohwada, Ken
- Applied Spectroscopy, Vol. 44, Issue 5
High-Valent Uranium Alkyls: Evidence for the Formation of U VI (CH 2 SiMe 3 ) 6
journal, August 2011
- Fortier, Skye; Walensky, Justin R.; Wu, Guang
- Journal of the American Chemical Society, Vol. 133, Issue 30
Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes
journal, December 2016
- King, David M.; Cleaves, Peter A.; Wooles, Ashley J.
- Nature Communications, Vol. 7, Issue 1
f-Orbital Mixing in the Octahedral f 2 Compounds UX 6 2– [X = F, Br, Cl, I] and PrCl 6 3–
journal, April 2020
- Edelstein, Norman M.; Lukens, Wayne W.
- The Journal of Physical Chemistry A, Vol. 124, Issue 21
Relativistic quantum chemical calculations show that the uranium molecule U2 has a quadruple bond
journal, October 2018
- Knecht, Stefan; Jensen, Hans Jørgen Aa.; Saue, Trond
- Nature Chemistry, Vol. 11, Issue 1
Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding
journal, April 2008
- Graves, Christopher R.; Yang, Ping; Kozimor, Stosh A.
- Journal of the American Chemical Society, Vol. 130, Issue 15
Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)
journal, April 2015
- Su, Jing; Dau, Phuong D.; Liu, Hong-Tao
- The Journal of Chemical Physics, Vol. 142, Issue 13
Homoleptic Aryl Complexes of Uranium (IV)
journal, July 2019
- Wolford, Nikki J.; Sergentu, Dumitru‐Claudiu; Brennessel, William W.
- Angewandte Chemie International Edition, Vol. 58, Issue 30
Energy-Degeneracy-Driven Covalency in Actinide Bonding
journal, December 2018
- Su, Jing; Batista, Enrique R.; Boland, Kevin S.
- Journal of the American Chemical Society, Vol. 140, Issue 51
Synthesis and electronic structure determination of uranium( vi ) ligand radical complexes
journal, January 2016
- Herasymchuk, Khrystyna; Chiang, Linus; Hayes, Cassandra E.
- Dalton Transactions, Vol. 45, Issue 31
- origin of the insulating state in uranium dioxide: X-ray absorption experiments and first-principles calculations
journal, April 2011
- Yu, S. -W.; Tobin, J. G.; Crowhurst, J. C.
- Physical Review B, Vol. 83, Issue 16
Analysis of the absorption spectra of complex pentavalent actinide halides: LiUF 6 , α‐NaUF 6 , and CsUF 6
journal, April 1986
- Hecht, H. G.; Malm, J. G.; Foropoulos, J.
- The Journal of Chemical Physics, Vol. 84, Issue 7
Characterization of SiaA, a Streptococcal Heme-Binding Protein Associated with a Heme ABC Transport System †
journal, February 2008
- Sook, Brian R.; Block, Darci R.; Sumithran, Suganya
- Biochemistry, Vol. 47, Issue 8