How to Bend the Uranyl Cation via Crystal Engineering

Carter, Korey and Kalaj, Mark and Kerridge, Andrew and Ridenour, J. August and Cahill, Christopher (2018) How to Bend the Uranyl Cation via Crystal Engineering. Inorganic Chemistry, 57 (5). pp. 2714-2723. ISSN 0020-1669

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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.

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Journal Article
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Inorganic Chemistry
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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
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20 Mar 2018 13:30
Last Modified:
16 Sep 2023 01:39