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Title: Intramolecular sensitization of americium luminescence in solution: Shining light on short-lived forbidden 5f transitions

In this study, the photophysical properties and solution thermodynamics of water soluble trivalent americium (AmIII) complexes formed with multidentate chromophore-bearing ligands, 3,4,3-LI(1,2-HOPO), Enterobactin, and 5-LIO(Me-3,2-HOPO), were investigated. The three chelators were shown to act as antenna chromophores for AmIII, generating sensitized luminescence emission from the metal upon complexation, with very short lifetimes ranging from 33 to 42 ns and low luminescence quantum yields (10–3 to 10–2%), characteristic of Near Infra-Red emitters in similar systems. The specific emission peak of AmIII assigned to the 5D17F1 f–f transition was exploited to characterize the high proton-independent stability of the complex formed with the most efficient sensitizer 3,4,3-LI(1,2-HOPO), with a log β110 = 20.4 ± 0.2 value. In addition, the optical and solution thermodynamic features of these AmIII complexes, combined with density functional theory calculations, were used to probe the influence of electronic structure on coordination properties across the f-element series and to gain insight into ligand field effects.
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Aix Marseille Univ., CNRS, Marseille (France)
Publication Date:
OSTI Identifier:
1246892
Report Number(s):
LA-UR--16-20418
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 165; Journal Issue: C; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY