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

Abstract

In this study, the photophysical properties and solution thermodynamics of water soluble trivalent americium (Am III) 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 Am III assigned to the 5D 17F 1 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 β 110 = 20.4 ± 0.2 value. In addition, the optical and solution thermodynamic features of these Am III 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). Chemical Sciences Division
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Aix-Marseille Univ., CNRS, CINaM UMR, Marseille (France)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1454447
Alternate Identifier(s):
OSTI ID: 1246892
Report Number(s):
LA-UR-16-20418
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:  
AC02-05CH11231; AC52-06NA25396
Resource 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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sturzbecher-Hoehne, M., Yang, P., D'Aleo, A., and Abergel, R. J. Intramolecular sensitization of americium luminescence in solution: Shining light on short-lived forbidden 5f transitions. United States: N. p., 2016. Web. doi:10.1039/C6DT00328A.
Sturzbecher-Hoehne, M., Yang, P., D'Aleo, A., & Abergel, R. J. Intramolecular sensitization of americium luminescence in solution: Shining light on short-lived forbidden 5f transitions. United States. doi:10.1039/C6DT00328A.
Sturzbecher-Hoehne, M., Yang, P., D'Aleo, A., and Abergel, R. J. Thu . "Intramolecular sensitization of americium luminescence in solution: Shining light on short-lived forbidden 5f transitions". United States. doi:10.1039/C6DT00328A. https://www.osti.gov/servlets/purl/1454447.
@article{osti_1454447,
title = {Intramolecular sensitization of americium luminescence in solution: Shining light on short-lived forbidden 5f transitions},
author = {Sturzbecher-Hoehne, M. and Yang, P. and D'Aleo, A. and Abergel, R. J.},
abstractNote = {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 5D1 → 7F1 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.},
doi = {10.1039/C6DT00328A},
journal = {Dalton Transactions},
number = C,
volume = 165,
place = {United States},
year = {2016},
month = {3}
}

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Figures / Tables:

Figure 1 Figure 1: Top: structures of 3,4,3-LI(1,2-HOPO) (1, left), Enterobactin (2, centre), and 5-LIO(Me-3,2-HOPO) (3, right). Bottom: simplified Jablonski diagram depicting the sensitization of EuIII, AmIII, and CmIII by the ligands 1, 2, and 3.

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    Works referencing / citing this record:

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