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Title: Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

Abstract

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences the composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1421980
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 49; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jin, Geng Bang, Lin, Jian, Estes, Shanna L., Skanthakumar, S., and Soderholm, L. Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example. United States: N. p., 2017. Web. doi:10.1021/jacs.7b09363.
Jin, Geng Bang, Lin, Jian, Estes, Shanna L., Skanthakumar, S., & Soderholm, L. Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example. United States. doi:10.1021/jacs.7b09363.
Jin, Geng Bang, Lin, Jian, Estes, Shanna L., Skanthakumar, S., and Soderholm, L. Fri . "Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example". United States. doi:10.1021/jacs.7b09363. https://www.osti.gov/servlets/purl/1421980.
@article{osti_1421980,
title = {Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example},
author = {Jin, Geng Bang and Lin, Jian and Estes, Shanna L. and Skanthakumar, S. and Soderholm, L.},
abstractNote = {Here, the influence of countercations (An+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of An+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A+ hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A+ counterions. Analyses of their chemical composition and solid-state structures demonstrate that A+ not only affects the overall solid-state packing of the Th–nitrato complexes but also influences the composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A+ hydration enthalpies, such that the A+ with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of An+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.},
doi = {10.1021/jacs.7b09363},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 139,
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 4 works
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Figures / Tables:

Figure 1 Figure 1: Monomeric Th-nitrato complexes, isolated in solids by evaporating aqueous solutions, shown as a function of countercation hydration enthalpies. A second [Th(NO3)4(H2O)4] complex, formed by the evaporation of Th-nitrate solutions containing relatively high HNO3 concentrations, follows the same trend and is omitted from the figure for clarity.

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Works referencing / citing this record:

CCDC 1810791: Experimental Crystal Structure Determination: TEQVIX : bis(tetramethylammonium) hexanitrato-thorium(iv)
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CCDC 1810792: Experimental Crystal Structure Determination: TEQVUJ : bis(tetraethylammonium) hexanitrato-thorium(iv)
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CCDC 1810793: Experimental Crystal Structure Determination: ZIYCER01 : bis(tetrabutylammonium) hexanitrato-thorium(iv)
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CCDC 1810797: Experimental Crystal Structure Determination: TEQWUK : bis(ammonium) hexanitrato-thorium(iv)
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CCDC 1810798: Experimental Crystal Structure Determination: TEQXAR : potassium diaqua-pentanitrato-thorium(iv) hydrate
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CCDC 1810799: Experimental Crystal Structure Determination: TEQXEV : potassium diaqua-pentanitrato-thorium(iv)
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CCDC 1810800: Experimental Crystal Structure Determination: TEQXIZ : di-potassium hexanitrato-thorium(iv)
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CCDC 1810801: Experimental Crystal Structure Determination: TEQXOF : tri-potassium hexanitrato-thorium(iv) nitric acid solvate trihydrate
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CCDC 1810802: Experimental Crystal Structure Determination: TEQXUL : lithium diaqua-pentanitrato-thorium(iv) hydrate
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CCDC 1810803: Experimental Crystal Structure Determination: TEQYAS : lithium diaqua-pentanitrato-thorium(iv) trihydrate
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Crystal Structure of Regularly T h -Symmetric [U(NO 3 ) 6 ] 2− Salts with Hydrogen Bond Polymers of Diamide Building Blocks
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  • Takao, Koichiro; Kazama, Hiroyuki; Ikeda, Yasuhisa
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Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations
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Crystal Structure of Regularly T h -Symmetric [U(NO 3 ) 6 ] 2− Salts with Hydrogen Bond Polymers of Diamide Building Blocks
journal, December 2018

  • Takao, Koichiro; Kazama, Hiroyuki; Ikeda, Yasuhisa
  • Angewandte Chemie International Edition, Vol. 58, Issue 1
  • DOI: 10.1002/anie.201811731

Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations
journal, January 2019


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.