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

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. As a result, the metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.
 [1] ;  [2] ;  [3] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [4] ;  [1] ;  [1] ;  [1] ;  [5] ;  [1] ;  [6] ;  [3] ;  [1] ;  [2] ;  [1]
  1. Florida State Univ., Tallahassee, FL (United States)
  2. The Univ. of Alabama, Tuscaloosa, AL (United States)
  3. National High Magnetic Field Lab., Tallahassee, FL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. National Institute for Materials Science, Ibaraki (Japan)
Publication Date:
OSTI Identifier:
Grant/Contract Number:
AC02-06CH11357; FG02-13ER16414
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Nature Publishing Group
Research Org:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY chemical sciences; inorganic chemistry