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  • IC_2017_03080F_Manuscript_AK

    Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright ©2018 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b03080

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    Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License

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How to Bend the Uranyl Cation via Crystal Engineering

Research output: Contribution to journalJournal article

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<mark>Journal publication date</mark>5/03/2018
<mark>Journal</mark>Inorganic Chemistry
Issue number5
Volume57
Number of pages10
Pages (from-to)2714-2723
Publication statusPublished
Early online date13/02/18
Original languageEnglish

Abstract

Bending the linear uranyl (UO22+) cation represents both a significant challenge and opportunity within the field of actinide hybrid materials. As part of related efforts to engage the nominally terminal oxo atoms of uranyl cation in noncovalent interactions, we synthesized a new uranyl complex, [UO2(C12H8N2)2(C7H2Cl3O2)2]·2H2O (complex 2), that featured both deviations from equatorial planarity and uranyl linearity from simple hydrothermal conditions. Based on this complex, we developed an approach to probe the nature and origin of uranyl bending within a family of hybrid materials, which was done via the synthesis of complexes 1–3 that display significant deviations from equatorial planarity and uranyl linearity (O–U–O bond angles between 162° and 164°) featuring 2,4,6-trihalobenzoic acid ligands (where Hal = F, Cl, and Br) and 1,10-phenanthroline, along with nine additional “nonbent” hybrid materials that either coformed with the “bent” complexes (4–6) or were prepared as part of complementary efforts to understand the mechanism(s) of uranyl bending (7–12). Complexes were characterized via single crystal X-ray diffraction and Raman, infrared (IR), and luminescence spectroscopy, as well as via quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analysis. Looking comprehensively, these results are compared with the small library of bent uranyl complexes in the literature, and herein we computationally demonstrate the origin of uranyl bending and delineate the energetics behind this process.

Bibliographic note

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright ©2018 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b03080