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

doi:10.1021/acs.inorgchem.7b00555

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

Abstract

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:

^[1]; Ivanov, Alexander S. ^[1];

^[1]; Sloop, Frederick V. ^[1]; Custelcean, Radu ^[1]; Popovs, Ilja ^[1]; Dekarske, Madeline M. ^[1]; Moyer, Bruce A. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

Publication Date:: 2017-05-04

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)

OSTI Identifier:: 1356918

Grant/Contract Number:: AC05-00OR22725; AC01-05CH11231

Resource 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)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    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., 2017. 
        Web.  doi:10.1021/acs.inorgchem.7b00555.

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                    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.

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                    Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., and Moyer, Bruce A. Thu .  
        "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.

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@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}

}

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DOI: 10.1021/acs.inorgchem.7b00555

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Figures / Tables:

Scheme 1: Structures of Soft N-Donor Ligands, BTBP and BTPhen, and Mixed N,O-Donor Ligands, BAPhen and BLPhen, in Their Preferred Conformations^a

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CCDC 1545803: Experimental Crystal Structure Determination: QAMQAZ : 2-hexyl-12-(hexyloxy)-3,4,9,10-tetraphenyldipyrido[3,4-b:4',3'-j][1,10]phenanthrolin-1(2H)-one methanol solvate monohydrate
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander; Bryantsev, Vyacheslav
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nwjmp

CCDC 1545804: Experimental Crystal Structure Determination: QAMQED : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-europium
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander; Bryantsev, Vyacheslav
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nwjnq

CCDC 1545805: Experimental Crystal Structure Determination: QAMQIH : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-gadolinium
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander; Bryantsev, Vyacheslav
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nwjpr

CCDC 1545806: Experimental Crystal Structure Determination: QAMQON : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-neodymium
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander; Bryantsev, Vyacheslav
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nwjqs

CCDC 1545807: Experimental Crystal Structure Determination: QAMQUT : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-praseodymium
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander; Bryantsev, Vyacheslav
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1nwjrt

CCDC 1545808: Experimental Crystal Structure Determination: QAMRAA : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-terbium Space Group: P 21/c (14), Cell: a 9.9062(7)Å b 21.5365(16)Å c 18.8918(15)Å, α 90.00° β 99.190(2)° γ 90.00°
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
The Cambridge Crystallographic Data Centre, vp
DOI: 10.5517/ccdc.csd.cc1nwjsv

CCDC 1545809: Experimental Crystal Structure Determination: 13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione methanol solvate monohydrate
dataset, April 2017

Jansone-Popova, Santa; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
The Cambridge Structural Database (CSD), vp
DOI: 10.5517/ccdc.csd.cc1nwjtw

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Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Furthermore, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.
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dataset (7)

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

Abstract

Citation Formats

Figures / Tables:

CCDC 1545803: Experimental Crystal Structure Determination: QAMQAZ : 2-hexyl-12-(hexyloxy)-3,4,9,10-tetraphenyldipyrido[3,4-b:4',3'-j][1,10]phenanthrolin-1(2H)-one methanol solvate monohydrate dataset, April 2017

CCDC 1545804: Experimental Crystal Structure Determination: QAMQED : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-europium dataset, April 2017

CCDC 1545805: Experimental Crystal Structure Determination: QAMQIH : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-gadolinium dataset, April 2017

CCDC 1545806: Experimental Crystal Structure Determination: QAMQON : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-neodymium dataset, April 2017

CCDC 1545807: Experimental Crystal Structure Determination: QAMQUT : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-praseodymium dataset, April 2017

CCDC 1545809: Experimental Crystal Structure Determination: 13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione methanol solvate monohydrate dataset, April 2017

CCDC 1545803: Experimental Crystal Structure Determination: QAMQAZ : 2-hexyl-12-(hexyloxy)-3,4,9,10-tetraphenyldipyrido[3,4-b:4',3'-j][1,10]phenanthrolin-1(2H)-one methanol solvate monohydrate
dataset, April 2017

CCDC 1545804: Experimental Crystal Structure Determination: QAMQED : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-europium
dataset, April 2017

CCDC 1545805: Experimental Crystal Structure Determination: QAMQIH : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-gadolinium
dataset, April 2017

CCDC 1545806: Experimental Crystal Structure Determination: QAMQON : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-neodymium
dataset, April 2017

CCDC 1545807: Experimental Crystal Structure Determination: QAMQUT : (13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione)-tris(nitrato)-praseodymium
dataset, April 2017

CCDC 1545809: Experimental Crystal Structure Determination: 13,18-dihexyl-1,2,3,4,4a,8b,9,10,11,12,12a,13,18,18a-tetradecahydro-1,4:9,12-dimethanodiquinolino[3,4-b:4',3'-j][1,10]phenanthroline-14,17-dione methanol solvate monohydrate
dataset, April 2017