ja8b10251_si_005.cif (3.46 MB)
Synthesis and Characterization of Tris-chelate Complexes for Understanding f‑Orbital Bonding in Later Actinides
dataset
posted on 2019-02-02, 00:30 authored by 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. BartAn isostructural
family of f-element compounds
(Ce, Nd, Sm, Gd; Am, Bk, Cf) of the redox-active dioxophenoxazine
ligand (DOPOq; DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate) was prepared.
This family, of the form M(DOPOq)3, represents
the first nonaqueous isostructural series, including the later actinides
berkelium and californium. The lanthanide derivatives were fully characterized
using 1H 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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redox-active dioxophenoxazine ligandUDFT-ZORA optimized structuresDOPO qbutyl -1-oxo Hcovalent character1 H NMR spectroscopyabsorption spectroscopyapproximationCASSCF analysiscaliforniumisostructural familyactinides berkeliumnonaqueous isostructural seriesTris-chelate ComplexesX-ray crystallographyelement compoundslanthanide derivativesphenoxazin -9-olateCASSCF calculationsSQUID magnetometryzeroth order
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