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Title: Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure

Abstract

Understanding of the nature and extent of chemical bonding in uranyl coordination complexes is crucial for the design of new ligands for nuclear waste separation, uranium extraction from seawater, and other applications. We report in this paper the synthesis, infrared spectroscopic characterization, and quantum chemical studies of a molecular uranyl–di-15-crown-5 complex. The structure and bonding of this unique complex featuring a distinctive 6-fold coplanar coordination staggered sandwich structure and an unusual non-perpendicular orientation of the uranyl moiety are evaluated using density functional theory and chemical bonding analyses. Finally, the results provide fundamental understanding of the coordination interaction of uranyl with oxygen-donor ligands.

Authors:
 [1];  [2];  [1];  [3];  [4];  [4];  [4];  [5]; ORCiD logo [1]
  1. Tsinghua Univ., Beijing (China). Dept. of Chemistry. Key Lab. of Organic Optoelectronics & Molecular Engineering of Ministry of Education
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  3. Duquesne Univ., Pittsburgh, PA (United States). Dept. of Chemistry and Biochemistry
  4. Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials. FELIX Lab.
  5. Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials. FELIX Lab.; Univ. of Amsterdam (Netherlands). Van't Hoff Inst. for Molecular Sciences
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Netherlands Organisation for Scientific Research (NWO)
OSTI Identifier:
1461101
Grant/Contract Number:  
AC02-05CH11231; 21433005; 91426302; 21590792; 724.011.002
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 52; Journal Issue: 86; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hu, Shu-Xian, Gibson, John K., Li, Wan-Lu, Van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Redlich, Britta, Oomens, Jos, and Li, Jun. Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure. United States: N. p., 2016. Web. doi:10.1039/c6cc07205d.
Hu, Shu-Xian, Gibson, John K., Li, Wan-Lu, Van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Redlich, Britta, Oomens, Jos, & Li, Jun. Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure. United States. https://doi.org/10.1039/c6cc07205d
Hu, Shu-Xian, Gibson, John K., Li, Wan-Lu, Van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Redlich, Britta, Oomens, Jos, and Li, Jun. Wed . "Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure". United States. https://doi.org/10.1039/c6cc07205d. https://www.osti.gov/servlets/purl/1461101.
@article{osti_1461101,
title = {Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure},
author = {Hu, Shu-Xian and Gibson, John K. and Li, Wan-Lu and Van Stipdonk, Michael J. and Martens, Jonathan and Berden, Giel and Redlich, Britta and Oomens, Jos and Li, Jun},
abstractNote = {Understanding of the nature and extent of chemical bonding in uranyl coordination complexes is crucial for the design of new ligands for nuclear waste separation, uranium extraction from seawater, and other applications. We report in this paper the synthesis, infrared spectroscopic characterization, and quantum chemical studies of a molecular uranyl–di-15-crown-5 complex. The structure and bonding of this unique complex featuring a distinctive 6-fold coplanar coordination staggered sandwich structure and an unusual non-perpendicular orientation of the uranyl moiety are evaluated using density functional theory and chemical bonding analyses. Finally, the results provide fundamental understanding of the coordination interaction of uranyl with oxygen-donor ligands.},
doi = {10.1039/c6cc07205d},
journal = {ChemComm},
number = 86,
volume = 52,
place = {United States},
year = {Wed Oct 05 00:00:00 EDT 2016},
month = {Wed Oct 05 00:00:00 EDT 2016}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Crystal structures of the dicyclohexyl-(18-crown-6) uranyl perchlorate complex and of its hydrolysis product
journal, January 1984


Natural population analysis
journal, July 1985

  • Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 2
  • DOI: 10.1063/1.449486

Bond Multiplicity in Transition-Metal Complexes: Applications of Two-Electron Valence Indices
journal, August 2008

  • Michalak, Artur; DeKock, Roger L.; Ziegler, Tom
  • The Journal of Physical Chemistry A, Vol. 112, Issue 31
  • DOI: 10.1021/jp800139g

Modified valence indices from the two-particle density matrix
journal, August 1994

  • Nalewajski, Roman F.; Mrozek, Janusz
  • International Journal of Quantum Chemistry, Vol. 51, Issue 4
  • DOI: 10.1002/qua.560510403

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O═U═O] 2+ Asymmetric Stretch
journal, March 2015

  • Gibson, John K.; Hu, Han-Shi; Van Stipdonk, Michael J.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 14
  • DOI: 10.1021/jp512599e

A simple measure of electron localization in atomic and molecular systems
journal, May 1990

  • Becke, A. D.; Edgecombe, K. E.
  • The Journal of Chemical Physics, Vol. 92, Issue 9
  • DOI: 10.1063/1.458517

Atomic reference energies for density functional calculations
journal, February 1997


Natural localized molecular orbitals
journal, August 1985

  • Reed, Alan E.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 4
  • DOI: 10.1063/1.449360

Photoelectron spectroscopy and the electronic structure of the uranyl tetrachloride dianion: UO 2 Cl 4 2−
journal, August 2012

  • Dau, Phuong Diem; Su, Jing; Liu, Hong-Tao
  • The Journal of Chemical Physics, Vol. 137, Issue 6
  • DOI: 10.1063/1.4742062

Synthesis and structural elucidation of novel uranyl-crown ether compounds isolated from nitric, hydrochloric, sulfuric, and acetic acids
journal, June 1991

  • Rogers, Robin D.; Bond, Andrew H.; Hipple, William G.
  • Inorganic Chemistry, Vol. 30, Issue 12
  • DOI: 10.1021/ic00012a021

f-Element/crown ether complexes, 11. Preparation and structural characterization of [UO2(OH2)5] [ClO4]2�3(15-crown-5)�CH3CN and [UO2(OH2)5] [ClO4]2�2(18-crown-6)�2 CH3CN�H2O
journal, October 1987

  • Rogers, Robin D.; Kurihara, Lynn K.; Benning, Matthew M.
  • Journal of Inclusion Phenomena, Vol. 5, Issue 5
  • DOI: 10.1007/BF00663006

The Free-Electron-Laser user facility FELIX
journal, January 1995

  • Oepts, D.; van der Meer, A. F. G.; van Amersfoort, P. W.
  • Infrared Physics & Technology, Vol. 36, Issue 1
  • DOI: 10.1016/1350-4495(94)00074-U

Crown Ether Complexes of Uranyl, Neptunyl, and Plutonyl: Hydration Differentiates Inclusion versus Outer Coordination
journal, May 2014

  • Gong, Yu; Gibson, John K.
  • Inorganic Chemistry, Vol. 53, Issue 11
  • DOI: 10.1021/ic500724q

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Self-consistent molecular Hartree—Fock—Slater calculations I. The computational procedure
journal, September 1973


Synthesis and Hydrolysis of Uranyl, Neptunyl, and Plutonyl Gas-Phase Complexes Exhibiting Discrete Actinide–Carbon Bonds
journal, April 2016


Crown ethers as actinide extractants in acidic aqueous biphasic systems: partitioning behavior in solution and crystallographic analyses of the solid state
journal, October 1994


Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

  • Van Lenthe, E.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 24, Issue 9
  • DOI: 10.1002/jcc.10255

Crown Ether Inclusion Complexes of the Early Actinide Elements, [AnO 2 (18-crown-6)] n + , An = U, Np, Pu and n = 1, 2: A Relativistic Density Functional Study
journal, March 2008

  • Shamov, Grigory A.; Schreckenbach, Georg; Martin, Richard L.
  • Inorganic Chemistry, Vol. 47, Issue 5
  • DOI: 10.1021/ic7015403

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

Bond Orbitals from Chemical Valence Theory
journal, March 2008

  • Michalak, Artur; Mitoraj, Mariusz; Ziegler, Tom
  • The Journal of Physical Chemistry A, Vol. 112, Issue 9
  • DOI: 10.1021/jp075460u

Crown Ethers:  Sensors for Ions and Molecular Scaffolds for Materials and Biological Models
journal, May 2004

  • Gokel, George W.; Leevy, W. Matthew; Weber, Michelle E.
  • Chemical Reviews, Vol. 104, Issue 5
  • DOI: 10.1021/cr020080k

Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements
journal, January 1987

  • Dolg, M.; Wedig, U.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 86, Issue 2
  • DOI: 10.1063/1.452288

The determination of molecular structures by density functional theory. The evaluation of analytical energy gradients by numerical integration
journal, January 1988

  • Versluis, Louis; Ziegler, Tom
  • The Journal of Chemical Physics, Vol. 88, Issue 1
  • DOI: 10.1063/1.454603

Structural identification of electron transfer dissociation products in mass spectrometry using infrared ion spectroscopy
journal, June 2016

  • Martens, Jonathan; Grzetic, Josipa; Berden, Giel
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11754

Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

Natural orbitals for chemical valence as descriptors of chemical bonding in transition metal complexes
journal, September 2006


Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988

  • Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
  • Chemical Reviews, Vol. 88, Issue 6
  • DOI: 10.1021/cr00088a005

Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955

  • Mulliken, R. S.
  • The Journal of Chemical Physics, Vol. 23, Issue 10
  • DOI: 10.1063/1.1740588

Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials
journal, January 2003

  • Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann
  • The Journal of Chemical Physics, Vol. 118, Issue 2
  • DOI: 10.1063/1.1521431

Two-electron valence indices from the Kohn-Sham orbitals
journal, January 1997


Segmented contraction scheme for small-core actinide pseudopotential basis sets
journal, March 2004


Observation and investigation of the uranyl tetrafluoride dianion (UO2F42−) and its solvation complexes with water and acetonitrile
journal, January 2012

  • Dau, Phuong Diem; Su, Jing; Liu, Hong-Tao
  • Chemical Science, Vol. 3, Issue 4
  • DOI: 10.1039/c2sc01052f

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Complexation of U(VI) with diphenyldithiophosphinic acid: spectroscopy, structure and DFT calculations
journal, April 2018

  • Meng, Dechao; Pu, Ning; Mei, Lei
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 317, Issue 1
  • DOI: 10.1007/s10967-018-5844-y

Theoretical studies on the oxidation states and electronic structures of actinide-borides: AnB 12 (An = Th–Cm) clusters
journal, January 2018

  • Hu, Shu-Xian; Chen, Mingyang; Ao, Bingyun
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 37
  • DOI: 10.1039/c8cp02561d