Probing Hydrogen and Halogen-Oxo Interactions in Uranyl Coordination Polymers:A Combined Crystallographic and Computational Study

Carter, Korey and Kalaj, Mark and Kerridge, Andrew and Cahill, Christopher (2018) Probing Hydrogen and Halogen-Oxo Interactions in Uranyl Coordination Polymers:A Combined Crystallographic and Computational Study. CrystEngComm, 20 (34). pp. 4916-4925. ISSN 1466-8033

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Abstract

The syntheses and crystal structures of four compounds containing the UO22+ cation and either benzoic acid (1), m-chlorobenzoic acid (2), m-bromobenzoic acid (3), or m-iodobenzoic acid (4) are described and the vibrational spectroscopic properties for compounds 3 and 4 are reported. Single crystal X-ray diffraction analysis of these materials shows that uranyl oxo atoms are engaged in non-covalent assembly via either hydrogen (1 and 2) or halogen bonding (3 and 4) interactions. The halogen bonding in compounds 3 and 4 is notable as the crystallographic metric percentage of the sum of the van der Waals radii indicates these interactions are of similar strength. Characteristics of the halogen-oxo interactions of 3 and 4 were probed via Raman and infrared spectroscopy, which revealed significant differences in stretching frequency values for the two compounds. Additionally, compounds 3 and 4 were characterized via quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analysis, which indicated that the I-oxo interaction in 4 is likely the stronger of the two interactions, with differences between the two interactions resulting from both inductive effects and halogen polarizability.

Item Type:
Journal Article
Journal or Publication Title:
CrystEngComm
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/3100/3104
Subjects:
ID Code:
126795
Deposited By:
Deposited On:
08 Aug 2018 15:08
Refereed?:
Yes
Published?:
Published
Last Modified:
30 May 2020 06:14