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A comprehensive approach for elucidating the interplay between 4fn+1 and 4fn5d1 configurations in Ln2+ complexes

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/d4sc05438e· OSTI ID:2496659
 [1];  [2];  [2];  [2];  [3];  [4]
  1. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
  2. Univ. of California, Irvine, CA (United States)
  3. Colorado School of Mines, Golden, CO (United States)
  4. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
Lanthanides (Ln) are typically found in the +3 oxidation state. However, in recent decades, their chemistry has been expanded to include the less stable +2 oxidation state across the entire series except promethium (Pm), facilitated by the coordination of ligands such as trimethylsilylcyclopentadienyl, C5H4SiMe3 (Cp'). The [LnCp'3] complexes have been the workhorse for the synthesis and theoretical study of the fundamental aspects of divalent lanthanide chemistry, where experimental and computational evidence have suggested the existence of different ground state (GS) configurations, 4fn+1 or 4fn5d1, depending on the specific metal. Standard reduction potentials and 4fn+1 to 4fn5d1 promotion energies have been two factors usually considered to rationalize the occurrence of these variable GS configurations, however the driving force behind this phenomenon is still not clear. In this work we present a comprehensive theoretical approach to shed light on this matter using the [LnCp3]- model systems. We begin by calculating 4fn+1 to 4fn5d1 promotion energies and successfully correlate them with existing experimental data. Furthermore, we analyze how changes in the GS charge distribution between the Ln ions, LnCp3 and the reduced [LnCp3]- complexes (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) correlate with experimental trends in redox potentials and the calculated promotion energies. For this purpose, a comprehensive theoretical work that includes relativistic ligand field density functional theory (LFDFT) and relativistic ab initio wavefunction methods was performed. This study will help the rational design of suitable environments to tune the different GS configurations as well as modulating the spectroscopic properties of new Ln2+ complexes.
Research Organization:
Colorado School of Mines, Golden, CO (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
89233218CNA000001; AC05-00OR22725; SC0023693
OSTI ID:
2496659
Alternate ID(s):
OSTI ID: 2538149
OSTI ID: 3005030
Report Number(s):
LA-UR--24-23990
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 16; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY