Synthesis and Characterization of Tris-chelate Complexes for Understanding f-Orbital Bonding in Later Actinides

Shane S. Galley, Scott A. Pattenaude, Carlo Alberto Gaggioli, Yusen Qiao, Joseph M. Sperling, Matthias Zeller, Srimanta Pakhira, Jose L. Mendoza-Cortes, Eric J. Schelter, Thomas E. Albrecht-Schmitt, Laura Gagliardi, Suzanne C. Bart

Research output: Contribution to journalArticle

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Abstract

An isostructural family of f-element compounds (Ce, Nd, Sm, Gd; Am, Bk, Cf) of the redox-active dioxophenoxazine ligand (DOPO q DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate) was prepared. This family, of the form M(DOPO q ) 3 , represents the first nonaqueous isostructural series, including the later actinides berkelium and californium. The lanthanide derivatives were fully characterized using 1 H NMR spectroscopy and SQUID magnetometry, while all species were structurally characterized by X-ray crystallography and electronic absorption spectroscopy. In order to probe the electronic structure of this new family, CASSCF calculations were performed and revealed these systems to be largely ionic in contrast to previous studies, where berkelium and californium typically have a small degree of covalent character. To validate the zeroth order regular approximation (ZORA) method, the same CASSCF analysis using experimental structures versus UDFT-ZORA optimized structures does not exhibit sizable changes in bonding patterns. This shows that UDFT-ZORA combined with CASSCF could be a useful first approximation to predict and investigate the structure and electronic properties of actinides and lanthanides that are difficult to synthesize or characterize.

Original languageEnglish (US)
JournalJournal of the American Chemical Society
DOIs
StatePublished - Jan 1 2019

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Berkelium
Californium
Actinoid Series Elements
Lanthanoid Series Elements
Actinides
Rare earth elements
Magnetometry
X ray crystallography
X Ray Crystallography
SQUIDs
Absorption spectroscopy
Chemical elements
Electronic properties
Nuclear magnetic resonance spectroscopy
Oxidation-Reduction
Electronic structure
Spectrum Analysis
Magnetic Resonance Spectroscopy
Ligands
Derivatives

PubMed: MeSH publication types

  • Journal Article

Cite this

Synthesis and Characterization of Tris-chelate Complexes for Understanding f-Orbital Bonding in Later Actinides. / Galley, Shane S.; Pattenaude, Scott A.; Gaggioli, Carlo Alberto; Qiao, Yusen; Sperling, Joseph M.; Zeller, Matthias; Pakhira, Srimanta; Mendoza-Cortes, Jose L.; Schelter, Eric J.; Albrecht-Schmitt, Thomas E.; Gagliardi, Laura; Bart, Suzanne C.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

Galley, SS, Pattenaude, SA, Gaggioli, CA, Qiao, Y, Sperling, JM, Zeller, M, Pakhira, S, Mendoza-Cortes, JL, Schelter, EJ, Albrecht-Schmitt, TE, Gagliardi, L & Bart, SC 2019, 'Synthesis and Characterization of Tris-chelate Complexes for Understanding f-Orbital Bonding in Later Actinides', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.8b10251
Galley, Shane S. ; Pattenaude, Scott A. ; Gaggioli, Carlo Alberto ; Qiao, Yusen ; Sperling, Joseph M. ; Zeller, Matthias ; Pakhira, Srimanta ; Mendoza-Cortes, Jose L. ; Schelter, Eric J. ; Albrecht-Schmitt, Thomas E. ; Gagliardi, Laura ; Bart, Suzanne C. / Synthesis and Characterization of Tris-chelate Complexes for Understanding f-Orbital Bonding in Later Actinides. In: Journal of the American Chemical Society. 2019.
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