A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an S = 11 Ground State
Abstract
The recent discovery of metal–metal bonding and valence delocalization in the dilanthanide complexes (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4fn5dz21 electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-valence clusters (CpiPr5)3Ln3H3I2 (1-Ln, Ln = Y, Gd), which were synthesized via potassium graphite reduction of the trivalent clusters (CpiPr5)3Ln3H3I3. Structural, computational, and spectroscopic analyses support valence delocalization in 1-Ln resulting from a three-center, one-electron σ bond formed from the 4dz2 and 5dz2 orbitals on Y and Gd, respectively. Dc magnetic susceptibility data obtained for 1-Gd reveal that valence delocalization engenders strong parallel alignment of the σ-bonding electron and the 4f electrons of each gadolinium center to afford a high-spin ground state of S = 11. Notably, this represents the first clear instance of metal–metal bonding in a molecular trilanthanide complex, and the large spin–spin exchange constant of J = 168(1) cm–1 determined for 1-Gd is only the second largest coupling constant characterized to date for a molecular lanthanide compound.
- Authors:
-
[1];
[4];
[3];
[5];
[1]
- Naval Air Warfare Center, Weapons Division, Research Department, Chemistry Division, US Navy, China Lake, California 93555, United States
- Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States
- Department of Chemistry, University of California, Davis, Davis, California 95616, United States
- Department of Chemistry, The University of Manchester, Manchester M13 9PL, U.K.
- Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States, Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States, Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
- Publication Date:
- Research Org.:
- University of California, Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF); ERC; National Institutes of Health (NIH)
- OSTI Identifier:
- 1971562
- Alternate Identifier(s):
- OSTI ID: 1971448
- Grant/Contract Number:
- AC02-05CH11231; CHE-2102603; STG-851504; 1R35GM126961-01
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 145 Journal Issue: 16; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; Cluster chemistry; Electron paramagnetic resonance spectroscopy; Lanthanides; Magnetic properties
Citation Formats
McClain, K. Randall, Kwon, Hyunchul, Chakarawet, Khetpakorn, Nabi, Rizwan, Kragskow, Jon G. C., Chilton, Nicholas F., Britt, R. David, Long, Jeffrey R., and Harvey, Benjamin G. A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an S = 11 Ground State. United States: N. p., 2023.
Web. doi:10.1021/jacs.3c00182.
McClain, K. Randall, Kwon, Hyunchul, Chakarawet, Khetpakorn, Nabi, Rizwan, Kragskow, Jon G. C., Chilton, Nicholas F., Britt, R. David, Long, Jeffrey R., & Harvey, Benjamin G. A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an S = 11 Ground State. United States. https://doi.org/10.1021/jacs.3c00182
McClain, K. Randall, Kwon, Hyunchul, Chakarawet, Khetpakorn, Nabi, Rizwan, Kragskow, Jon G. C., Chilton, Nicholas F., Britt, R. David, Long, Jeffrey R., and Harvey, Benjamin G. Mon .
"A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an S = 11 Ground State". United States. https://doi.org/10.1021/jacs.3c00182.
@article{osti_1971562,
title = {A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an S = 11 Ground State},
author = {McClain, K. Randall and Kwon, Hyunchul and Chakarawet, Khetpakorn and Nabi, Rizwan and Kragskow, Jon G. C. and Chilton, Nicholas F. and Britt, R. David and Long, Jeffrey R. and Harvey, Benjamin G.},
abstractNote = {The recent discovery of metal–metal bonding and valence delocalization in the dilanthanide complexes (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4fn5dz21 electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-valence clusters (CpiPr5)3Ln3H3I2 (1-Ln, Ln = Y, Gd), which were synthesized via potassium graphite reduction of the trivalent clusters (CpiPr5)3Ln3H3I3. Structural, computational, and spectroscopic analyses support valence delocalization in 1-Ln resulting from a three-center, one-electron σ bond formed from the 4dz2 and 5dz2 orbitals on Y and Gd, respectively. Dc magnetic susceptibility data obtained for 1-Gd reveal that valence delocalization engenders strong parallel alignment of the σ-bonding electron and the 4f electrons of each gadolinium center to afford a high-spin ground state of S = 11. Notably, this represents the first clear instance of metal–metal bonding in a molecular trilanthanide complex, and the large spin–spin exchange constant of J = 168(1) cm–1 determined for 1-Gd is only the second largest coupling constant characterized to date for a molecular lanthanide compound.},
doi = {10.1021/jacs.3c00182},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 145,
place = {United States},
year = {Mon Apr 17 00:00:00 EDT 2023},
month = {Mon Apr 17 00:00:00 EDT 2023}
}
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Works referenced in this record:
Atomic parameters for paramagnetic resonance data
journal, June 1978
- Morton, J. R.; Preston, K. F.
- Journal of Magnetic Resonance (1969), Vol. 30, Issue 3
Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II)
journal, May 2012
- MacDonald, Matthew R.; Bates, Jefferson E.; Fieser, Megan E.
- Journal of the American Chemical Society, Vol. 134, Issue 20
Strong Electronic and Magnetic Coupling in M 4 (M = Ni, Cu) Clusters via Direct Orbital Interactions between Low-Coordinate Metal Centers
journal, October 2020
- Chakarawet, Khetpakorn; Atanasov, Mihail; Marbey, Jonathan
- Journal of the American Chemical Society, Vol. 142, Issue 45
Synthesis and Redox Properties of Triiron Complexes Featuring Strong Fe-Fe Interactions
journal, January 2011
- Zhao, Qinliang; Betley, Theodore A.
- Angewandte Chemie International Edition, Vol. 50, Issue 3
Large Anisotropy Barrier in a Tetranuclear Single-Molecule Magnet Featuring Low-Coordinate Cobalt Centers
journal, February 2018
- Chakarawet, Khetpakorn; Bunting, Philip C.; Long, Jeffrey R.
- Journal of the American Chemical Society, Vol. 140, Issue 6
Assessing the Metal–Metal Interactions in a Series of Heterobimetallic Nb/M Complexes (M = Fe, Co, Ni, Cu) and Their Effect on Multielectron Redox Properties
journal, December 2018
- Barden, Brett A.; Culcu, Gursu; Krogman, Jeremy P.
- Inorganic Chemistry, Vol. 58, Issue 1
Optical transitions of symmetrical mixed-valence systems in the Class II–III transition regimeElectronic supplementary information (ESI) is available: derivation of eqn. (39c), table summarizing the relationships between band maxima and band widths predicted by the two-state model and table of spectral properties of mixed-valence ruthenium(II)/(III) bridged by pyrazine and dicyanamide. See http://www.rsc.org/suppdata/cs/b0/b008034i/
journal, April 2002
- Brunschwig, Bruce S.; Creutz, Carol; Sutin, Norman
- Chemical Society Reviews, Vol. 31, Issue 3
PHI: A powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d - and f -block complexes
journal, February 2013
- Chilton, Nicholas F.; Anderson, Russell P.; Turner, Lincoln D.
- Journal of Computational Chemistry, Vol. 34, Issue 13
Evaluating electrochemical accessibility of 4fn5d1 and 4fn+1 Ln(ii ) ions in (C5H4SiMe3)3Ln and (C5Me4H)3Ln complexes
journal, January 2021
- Trinh, Michael T.; Wedal, Justin C.; Evans, William J.
- Dalton Transactions, Vol. 50, Issue 40
Metal–Metal Bonds in Catalysis
journal, December 2016
- Powers, Ian G.; Uyeda, Christopher
- ACS Catalysis, Vol. 7, Issue 2
Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding
journal, January 2022
- Gould, Colin A.; McClain, K. Randall; Reta, Daniel
- Science, Vol. 375, Issue 6577
Single-Electron Lanthanide-Lanthanide Bonds Inside Fullerenes toward Robust Redox-Active Molecular Magnets
journal, September 2019
- Liu, Fupin; Spree, Lukas; Krylov, Denis S.
- Accounts of Chemical Research, Vol. 52, Issue 10
Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of Terbium(II) and Dysprosium(II)
journal, August 2019
- Gould, Colin A.; McClain, K. Randall; Yu, Jason M.
- Journal of the American Chemical Society, Vol. 141, Issue 33
Meta-Atom Behavior in Clusters Revealing Large Spin Ground States
journal, October 2015
- Hernández Sánchez, Raúl; Betley, Theodore A.
- Journal of the American Chemical Society, Vol. 137, Issue 43
A rare earth metallocene containing a 2,2′-azopyridyl radical anion
journal, January 2021
- Delano IV, Francis; Castellanos, Ernesto; McCracken, John
- Chemical Science, Vol. 12, Issue 46
Thermally Persistent High-Spin Ground States in Octahedral Iron Clusters
journal, November 2018
- Sánchez, Raúl Hernández; Betley, Theodore A.
- Journal of the American Chemical Society, Vol. 140, Issue 48
[( H L) 2 Fe 6 (NCMe) m ] n + ( m = 0, 2, 4, 6; n = −1, 0, 1, 2, 3, 4, 6): An Electron-Transfer Series Featuring Octahedral Fe 6 Clusters Supported by a Hexaamide Ligand Platform
journal, June 2011
- Zhao, Qinliang; Harris, T. David; Betley, Theodore A.
- Journal of the American Chemical Society, Vol. 133, Issue 21
Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln 2+ Ions in the [K(2.2.2-cryptand)][(C 5 H 4 SiMe 3 ) 3 Ln] Complexes: The Variable Nature of Dy 2+ and Nd 2+
journal, December 2014
- Fieser, Megan E.; MacDonald, Matthew R.; Krull, Brandon T.
- Journal of the American Chemical Society, Vol. 137, Issue 1
ELDOR-detected NMR: A general and robust method for electron-nuclear hyperfine spectroscopy?
journal, July 2017
- Cox, Nicholas; Nalepa, Anna; Lubitz, Wolfgang
- Journal of Magnetic Resonance, Vol. 280
Maximizing Electron Exchange in a [Fe 3 ] Cluster
journal, February 2016
- Hernández Sánchez, Raúl; Bartholomew, Amymarie K.; Powers, Tamara M.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Intervalence-Transfer Absorption. Part 2. Theoretical Considerations and Spectroscopic Data
book, January 2007
- Hush, N. S.
- Progress in Inorganic Chemistry
Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions
journal, January 2006
- D'Alessandro, Deanna M.; Keene, F. Richard
- Chemical Society Reviews
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr 2+ , Gd 2+ , Tb 2+ , and Lu 2+
journal, May 2013
- MacDonald, Matthew R.; Bates, Jefferson E.; Ziller, Joseph W.
- Journal of the American Chemical Society, Vol. 135, Issue 26
Electron-transfer and f-d absorption bands of some lanthanide and actinide complexes and the standard (II-III) oxidation potential for each member of the lanthanide and actinide series
journal, June 1973
- Nugent, L. J.; Baybarz, R. D.; Burnett, J. L.
- The Journal of Physical Chemistry, Vol. 77, Issue 12
Synthesis and reductive chemistry of bimetallic and trimetallic rare-earth metallocene hydrides with (C5H4SiMe3)1− ligands
journal, November 2017
- Dumas, Megan T.; Chen, Guo P.; Hu, Jasper Y.
- Journal of Organometallic Chemistry, Vol. 849-850
Engineering electronic structure to prolong relaxation times in molecular qubits by minimising orbital angular momentum
journal, July 2019
- Ariciu, Ana-Maria; Woen, David H.; Huh, Daniel N.
- Nature Communications, Vol. 10, Issue 1