Emergence of californium as the second transitional element in the actinide series

Samantha K. Cary, Monica Vasiliu, Ryan E. Baumbach, Jared T. Stritzinger, Thomas D. Green, Kariem Diefenbach, Justin N. Cross, Kenneth L. Knappenberger, Guokui Liu, Mark A. Silver, A. Eugene Deprince, Matthew J. Polinski, Shelley M. Van Cleve, Jane H. House, Naoki Kikugawa, Andrew Gallagher, Alexandra A. Arico, David A. Dixon, Thomas E. Albrecht-Schmitt

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105 Scopus citations

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.

Original languageEnglish (US)
Article number6827
JournalNature communications
Volume6
DOIs
StatePublished - Apr 16 2015

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Biochemistry, Genetics and Molecular Biology
  • General Physics and Astronomy

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