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Title: Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

Abstract

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 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(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II 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(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5dmore » 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1];  [5]; ORCiD logo [2]
  1. Univ. of California, Irvine, CA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Wisconsin, Madison, WI (United States)
  4. Stanford Univ., Palo Alto, CA (United States)
  5. 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. 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, and Yang, Ping. Fri . "Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31– using XANES spectroscopy and DFT calculations". United States. doi: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 = {2017},
month = {6}
}

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