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Title: Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

Abstract

Synthetic strategies to glean molecular complexes of high-valent lanthanides, other than the ubiquitous Ce4+ ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and the solid state is essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an S4 symmetric, four-coordinate tetravalent terbium complex, [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (where Et is ethyl and tBu is tert-butyl). The ligand field in this complex is weak and the metal–ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et2O)K][Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4]. The crucial stability of the tetravalent complex enables its thorough characterization. The stepwise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XANES), and density functional theory studies indicate a 4ƒ7 ground state for [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] with considerable zero-fieldmore » splitting, demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal–ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (measured by Tb L3-edge XAS) to that observed in TbO2 implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Roosevelt Univ., Chicago, IL (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE National Nuclear Security Administration (NNSA); National Institutes of Health (NIH)
OSTI Identifier:
1558225
Report Number(s):
LA-UR-19-26027
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
89233218CNA000001; AC02-76SF00515; SC0019385
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 33; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rice, Natalie T., Popov, Ivan A., Russo, Dominic R., Bacsa, John, Batista, Enrique R., Yang, Ping, Telser, Joshua, and La Pierre, Henry S. Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex. United States: N. p., 2019. Web. doi:10.1021/jacs.9b06622.
Rice, Natalie T., Popov, Ivan A., Russo, Dominic R., Bacsa, John, Batista, Enrique R., Yang, Ping, Telser, Joshua, & La Pierre, Henry S. Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex. United States. https://doi.org/10.1021/jacs.9b06622
Rice, Natalie T., Popov, Ivan A., Russo, Dominic R., Bacsa, John, Batista, Enrique R., Yang, Ping, Telser, Joshua, and La Pierre, Henry S. Sun . "Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex". United States. https://doi.org/10.1021/jacs.9b06622. https://www.osti.gov/servlets/purl/1558225.
@article{osti_1558225,
title = {Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex},
author = {Rice, Natalie T. and Popov, Ivan A. and Russo, Dominic R. and Bacsa, John and Batista, Enrique R. and Yang, Ping and Telser, Joshua and La Pierre, Henry S.},
abstractNote = {Synthetic strategies to glean molecular complexes of high-valent lanthanides, other than the ubiquitous Ce4+ ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and the solid state is essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an S4 symmetric, four-coordinate tetravalent terbium complex, [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (where Et is ethyl and tBu is tert-butyl). The ligand field in this complex is weak and the metal–ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et2O)K][Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4]. The crucial stability of the tetravalent complex enables its thorough characterization. The stepwise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XANES), and density functional theory studies indicate a 4ƒ7 ground state for [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] with considerable zero-field splitting, demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal–ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (measured by Tb L3-edge XAS) to that observed in TbO2 implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.},
doi = {10.1021/jacs.9b06622},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 141,
place = {United States},
year = {2019},
month = {7}
}

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Figures / Tables:

Figure 1 Figure 1: Synthesis and structure of terbium imidophosphorane complexes. (A) Resonance structures in tris(piperidinyl)imidophosphorane ligand. (B) Resonance structures in 2. (C) Hyperconjugation in 2. (D) Synthesis of 4 from 3. (E) X-ray crystal structures of 3 and 4 with thermal ellipsoids at 50% probability. Black, blue, yellow, red, green, andmore » aqua represent carbon, nitrogen, phosphorous, oxygen, potassium, and terbium, respectively. Metrical data for Tb–N and P–N distances and Tb–N–P angles in each complex.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.