title: Unusual structure, bonding and properties in a californium borate.
abstract: The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Polinski
authors.affiliation: Department of Chemistry, The University of Alabama, Shelby Hall, Tuscaloosa Alabama 35487, USA.
authors.forename: Edward B
authors.initials: EB
authors.lastname: Garner
authors.affiliation: 1] Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA [2] SUBATECH, Unité Mixte de Recherche 6457, Centre National de la Recherche Scientifique, Institut National de Physique Nucléaire et de Physique des Particules, Ecole des Mines de Nantes, Université de Nantes, 4 rue Alfred Kastler, BP20722, 44307 Nantes Cédex 3, France.
authors.forename: Rémi
authors.initials: R
authors.lastname: Maurice
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
authors.forename: Nora
authors.initials: N
authors.lastname: Planas
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Jared T
authors.initials: JT
authors.lastname: Stritzinger
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: T Gannon
authors.initials: TG
authors.lastname: Parker
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Justin N
authors.initials: JN
authors.lastname: Cross
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Thomas D
authors.initials: TD
authors.lastname: Green
authors.affiliation: 1] Institute for Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, 52428 Jülich, Germany [2] Institut für Kristallographie, Rheinisch-Westfaelische Technische Hochschule Aachen University, 52066 Aachen, Germany.
authors.forename: Evgeny V
authors.initials: EV
authors.lastname: Alekseev
authors.affiliation: Nuclear Materials Processing Group, Oak Ridge National Laboratory, One Bethel Valley Rd, Oak Ridge, Tennessee 37830, USA.
authors.forename: Shelley M
authors.initials: SM
authors.lastname: Van Cleve
authors.affiliation: Institut für Geowissenschaften, Universität Kiel, 24118 Kiel, Germany.
authors.forename: Wulf
authors.initials: W
authors.lastname: Depmeier
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Michael
authors.initials: M
authors.lastname: Shatruk
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Kenneth L
authors.initials: KL
authors.lastname: Knappenberger
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
authors.forename: Guokui
authors.initials: G
authors.lastname: Liu
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
authors.forename: S
authors.initials: S
authors.lastname: Skanthakumar
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
authors.forename: Lynda
authors.initials: L
authors.lastname: Soderholm
authors.affiliation: Department of Chemistry, The University of Alabama, Shelby Hall, Tuscaloosa Alabama 35487, USA.
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Albrecht-Schmitt
mesh_terms: D001881:Borates / Q000737:chemistry*; D002142:Californium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008163:Luminescent Measurements; D008958:Models, Molecular; D015394:Molecular Structure; D013696:Temperature
chemical_list: D001881:Borates; D008024:Ligands; D002142:Californium
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