Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31– using XANES spectroscopy and DFT calculations
Abstract
Here, the isolation of [K(2.2.2-cryptand)][Ln(C5H4SiMe3)3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C5H4SiMe3)31– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular LnII complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-order perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C5H4SiMe3)31– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f6 5d0 (SmII), 4f13 5d0 (TmII), 4f14 5d0 (YbII), 4f14 5d1 (LuII), and 4d1 (YII) electronic configurations. Additionally, our results suggest that Ln(C5H4SiMe3)31– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain LnII ions, but with 4fn 5d1 configurations (not 4fn+1 5d0). In these 4fn 5d1 complexes, the C3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4fn 5d1 electronic configurations lower in energy than the more typical 4fn+1 5d0 configuration.
- Authors:
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- Univ. of California, Irvine, CA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Wisconsin, Madison, WI (United States)
- Stanford Univ., Palo Alto, CA (United States)
- Karlsruhe Institute of Technology, Karlsruhe (Germany)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1398908
- Report Number(s):
- LA-UR-16-20691
Journal ID: ISSN 2041-6520; CSHCBM
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry
Citation Formats
Fieser, Megan E., Ferrier, Maryline Ghislaine, Su, Jing, Batista, Enrique Ricardo, Cary, Samantha K., Engle, Jonathan Ward, Evans, William J., Lezama Pacheco, Juan S., Kozimor, Stosh A., Olson, Angela Christine, Ryan, Austin J., Stein, Benjamin W., Wagner, Gregory Lawrence, Woen, David H., Vitova, Tonya, and Yang, Ping. Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31– using XANES spectroscopy and DFT calculations. United States: N. p., 2017.
Web. doi:10.1039/C7SC00825B.
Fieser, Megan E., Ferrier, Maryline Ghislaine, Su, Jing, Batista, Enrique Ricardo, Cary, Samantha K., Engle, Jonathan Ward, Evans, William J., Lezama Pacheco, Juan S., Kozimor, Stosh A., Olson, Angela Christine, Ryan, Austin J., Stein, Benjamin W., Wagner, Gregory Lawrence, Woen, David H., Vitova, Tonya, & Yang, Ping. Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31– using XANES spectroscopy and DFT calculations. United States. https://doi.org/10.1039/C7SC00825B
Fieser, Megan E., Ferrier, Maryline Ghislaine, Su, Jing, Batista, Enrique Ricardo, Cary, Samantha K., Engle, Jonathan Ward, Evans, William J., Lezama Pacheco, Juan S., Kozimor, Stosh A., Olson, Angela Christine, Ryan, Austin J., Stein, Benjamin W., Wagner, Gregory Lawrence, Woen, David H., Vitova, Tonya, and Yang, Ping. Fri .
"Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31– using XANES spectroscopy and DFT calculations". United States. https://doi.org/10.1039/C7SC00825B. https://www.osti.gov/servlets/purl/1398908.
@article{osti_1398908,
title = {Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31– using XANES spectroscopy and DFT calculations},
author = {Fieser, Megan E. and Ferrier, Maryline Ghislaine and Su, Jing and Batista, Enrique Ricardo and Cary, Samantha K. and Engle, Jonathan Ward and Evans, William J. and Lezama Pacheco, Juan S. and Kozimor, Stosh A. and Olson, Angela Christine and Ryan, Austin J. and Stein, Benjamin W. and Wagner, Gregory Lawrence and Woen, David H. and Vitova, Tonya and Yang, Ping},
abstractNote = {Here, the isolation of [K(2.2.2-cryptand)][Ln(C5H4SiMe3)3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C5H4SiMe3)31– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular LnII complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-order perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C5H4SiMe3)31– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f6 5d0 (SmII), 4f13 5d0 (TmII), 4f14 5d0 (YbII), 4f14 5d1 (LuII), and 4d1 (YII) electronic configurations. Additionally, our results suggest that Ln(C5H4SiMe3)31– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain LnII ions, but with 4fn 5d1 configurations (not 4fn+1 5d0). In these 4fn 5d1 complexes, the C3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4fn 5d1 electronic configurations lower in energy than the more typical 4fn+1 5d0 configuration.},
doi = {10.1039/C7SC00825B},
journal = {Chemical Science},
number = 9,
volume = 8,
place = {United States},
year = {Fri Jun 30 00:00:00 EDT 2017},
month = {Fri Jun 30 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
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