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Title: Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency

Here, we report a new family of preorganized bislactam- 1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent fblock metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state. DFT calculations further elaborate on the variety of effects that dictate the performance of these preorganized compounds.
Authors:
ORCiD logo [1] ;  [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Grant/Contract Number:
AC05-00OR22725; AC01-05CH11231
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 10; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1356918

Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., and Moyer, Bruce A.. Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency. United States: N. p., Web. doi:10.1021/acs.inorgchem.7b00555.
Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., & Moyer, Bruce A.. Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency. United States. doi:10.1021/acs.inorgchem.7b00555.
Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., and Moyer, Bruce A.. 2017. "Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency". United States. doi:10.1021/acs.inorgchem.7b00555. https://www.osti.gov/servlets/purl/1356918.
@article{osti_1356918,
title = {Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency},
author = {Jansone-Popova, Santa and Ivanov, Alexander S. and Bryantsev, Vyacheslav S. and Sloop, Frederick V. and Custelcean, Radu and Popovs, Ilja and Dekarske, Madeline M. and Moyer, Bruce A.},
abstractNote = {Here, we report a new family of preorganized bislactam- 1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent fblock metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state. DFT calculations further elaborate on the variety of effects that dictate the performance of these preorganized compounds.},
doi = {10.1021/acs.inorgchem.7b00555},
journal = {Inorganic Chemistry},
number = 10,
volume = 56,
place = {United States},
year = {2017},
month = {5}
}