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 language | English (US) |
|---|---|
| Journal | Journal of the American Chemical Society |
| DOIs | |
| State | Published - Jan 1 2019 |
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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 journal › Article
}
TY - JOUR
T1 - Synthesis and Characterization of Tris-chelate Complexes for Understanding f-Orbital Bonding in Later Actinides
AU - Galley, Shane S.
AU - Pattenaude, Scott A.
AU - Gaggioli, Carlo Alberto
AU - Qiao, Yusen
AU - Sperling, Joseph M.
AU - Zeller, Matthias
AU - Pakhira, Srimanta
AU - Mendoza-Cortes, Jose L.
AU - Schelter, Eric J.
AU - Albrecht-Schmitt, Thomas E.
AU - Gagliardi, Laura
AU - Bart, Suzanne C.
PY - 2019/1/1
Y1 - 2019/1/1
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.8b10251
DO - 10.1021/jacs.8b10251
M3 - Article
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
ER -