title: Emergence of californium as the second transitional element in the actinide series.
abstract: A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Samantha K
authors.initials: SK
authors.lastname: Cary
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487, USA.
authors.forename: Monica
authors.initials: M
authors.lastname: Vasiliu
authors.affiliation: National High Magnetic Field Laboratory, Tallahassee, Florida 32310, USA.
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Baumbach
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: Thomas D
authors.initials: TD
authors.lastname: Green
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Kariem
authors.initials: K
authors.lastname: Diefenbach
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: Kenneth L
authors.initials: KL
authors.lastname: Knappenberger
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Guokui
authors.initials: G
authors.lastname: Liu
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Silver
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: A Eugene
authors.initials: AE
authors.lastname: DePrince
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: Nuclear Materials Processing Group, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, USA.
authors.forename: Shelley M
authors.initials: SM
authors.lastname: Van Cleve
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Jane H
authors.initials: JH
authors.lastname: House
authors.affiliation: National Institute for Materials Science, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Naoki
authors.initials: N
authors.lastname: Kikugawa
authors.affiliation: National High Magnetic Field Laboratory, Tallahassee, Florida 32310, USA.
authors.forename: Andrew
authors.initials: A
authors.lastname: Gallagher
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Alexandra A
authors.initials: AA
authors.lastname: Arico
authors.affiliation: Department of Chemistry, The University of Alabama, 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