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Title: Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution

Abstract

Two thorium(IV) compounds, [Th(H 2O) 4Cl 4]·2 (HPy·Cl) ( 1) and (HPy) 3[Th 3(H 2O) 2Cl 10(OH) 5]·4(HPy·Cl) ( 2) (HPy = pyridinium), were isolated from acidic aqueous solution. The compounds were synthesized at room temperature and subsequently characterized using single crystal X-ray diffraction along with Raman and IR spectroscopies. Whereas compound 1 is built from discrete mononuclear Th(H 2O) 4Cl 4 units, compound 2 consists of a novel hydroxo-bridged trimeric [Th 3(OH) 5] 7+ core. Such species are largely absent from discussions of Th solution and solid-state chemistry and their isolation may be attributed to outer coordination sphere interactions that help stabilize the structural units; extensive hydrogen bonding and $π–π$ stacking interactions are present in 1 and 2. Density functional theory calculations were performed to predict the respective vibrational frequencies of the structural units, and their relative stability was predicted at the correlated molecular theory level. Small-angle X-ray scattering analysis of [Th 3(OH) 5] 7+ in water indicates that the trimeric structural unit remains intact and that it is indeed an important species that necessitates consideration in geochemical models and for design of Th materials from water.

Authors:
 [1];  [2];  [3];  [1];  [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Georgetown Univ., Washington, D.C. (United States). Dept. of Chemistry
  2. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
  3. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1561850
Grant/Contract Number:  
NA0003763
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 16; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Wacker, Jennifer N., Vasiliu, Monica, Colliard, Ian, Ayscue III, R. Lee, Han, Sae Young, Bertke, Jeffery A., Nyman, May, Dixon, David A., and Knope, Karah E. Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b01238.
Wacker, Jennifer N., Vasiliu, Monica, Colliard, Ian, Ayscue III, R. Lee, Han, Sae Young, Bertke, Jeffery A., Nyman, May, Dixon, David A., & Knope, Karah E. Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution. United States. doi:10.1021/acs.inorgchem.9b01238.
Wacker, Jennifer N., Vasiliu, Monica, Colliard, Ian, Ayscue III, R. Lee, Han, Sae Young, Bertke, Jeffery A., Nyman, May, Dixon, David A., and Knope, Karah E. Sat . "Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution". United States. doi:10.1021/acs.inorgchem.9b01238.
@article{osti_1561850,
title = {Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution},
author = {Wacker, Jennifer N. and Vasiliu, Monica and Colliard, Ian and Ayscue III, R. Lee and Han, Sae Young and Bertke, Jeffery A. and Nyman, May and Dixon, David A. and Knope, Karah E.},
abstractNote = {Two thorium(IV) compounds, [Th(H2O)4Cl4]·2 (HPy·Cl) (1) and (HPy)3[Th3(H2O)2Cl10(OH)5]·4(HPy·Cl) (2) (HPy = pyridinium), were isolated from acidic aqueous solution. The compounds were synthesized at room temperature and subsequently characterized using single crystal X-ray diffraction along with Raman and IR spectroscopies. Whereas compound 1 is built from discrete mononuclear Th(H2O)4Cl4 units, compound 2 consists of a novel hydroxo-bridged trimeric [Th3(OH)5]7+ core. Such species are largely absent from discussions of Th solution and solid-state chemistry and their isolation may be attributed to outer coordination sphere interactions that help stabilize the structural units; extensive hydrogen bonding and $π–π$ stacking interactions are present in 1 and 2. Density functional theory calculations were performed to predict the respective vibrational frequencies of the structural units, and their relative stability was predicted at the correlated molecular theory level. Small-angle X-ray scattering analysis of [Th3(OH)5]7+ in water indicates that the trimeric structural unit remains intact and that it is indeed an important species that necessitates consideration in geochemical models and for design of Th materials from water.},
doi = {10.1021/acs.inorgchem.9b01238},
journal = {Inorganic Chemistry},
number = 16,
volume = 58,
place = {United States},
year = {2019},
month = {6}
}

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Works referencing / citing this record:

Tetranuclear oxido-bridged thorium( iv ) clusters obtained using tridentate Schiff bases
journal, January 2019

  • Tsantis, Sokratis T.; Lagou-Rekka, Aimilia; Konidaris, Konstantis F.
  • Dalton Transactions, Vol. 48, Issue 41
  • DOI: 10.1039/c9dt03189h