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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b10251· OSTI ID:1543729
 [1];  [2];  [3];  [4];  [1];  [2];  [5];  [5];  [4];  [1];  [3];  [2]
  1. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
  2. H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States
  3. Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, Minnesota 55455, United States
  4. P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
  5. Department of Physics, Scientific Computing, Material Sciences and Engineering, High-Performance Material Institute &, Condensed Matter Theory - High Magnetic Field National Laboratory, Florida State University, Tallahassee, Florida 32310, United States; Department of Chemical &, Biomedical Engineering, Florida A&,M University − Florida State University, Joint College of Engineering, Tallahassee, Florida 32310, United States
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An 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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Florida State Univ., Tallahassee, FL (United States); Purdue Univ., West Lafayette, IN (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
DOE Contract Number:
AC02-05CH11231; SC0010677; SC0008479; SC0017259
OSTI ID:
1543729
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

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