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

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.; Skanthakumar, S.; Soderholm, L.

doi:10.1021/jacs.7b09363

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

Journal Article · 17 November 2017 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.7b09363 · OSTI ID:1421980

^[1];

^[1]; Skanthakumar, S. ^[1];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1421980

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 49; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations Estes, Shanna L.; Qiao, Baofu; Jin, Geng Bang Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07982-5	journal	January 2019
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