Journal article
Probing hydrogen and halogen-oxo interactions in uranyl coordination polymers: a combined crystallographic and computational study
CrystEngComm, Vol.20(34), pp.4916-4925
2018
DOI: 10.1039/C8CE00682B
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.
Details
- Title: Subtitle
- Probing hydrogen and halogen-oxo interactions in uranyl coordination polymers: a combined crystallographic and computational study
- Creators
- Korey P Carter - Department of Chemistry, The George Washington University, Washington, D.C. 20052, USAMark Kalaj - Department of Chemistry, The George Washington University, Washington, D.C. 20052, USAAndrew Kerridge - Department of Chemistry, Lancaster University, Lancaster LA1 4YB, UKChristopher L Cahill - Department of Chemistry, The George Washington University, Washington, D.C. 20052, USA
- Resource Type
- Journal article
- Publication Details
- CrystEngComm, Vol.20(34), pp.4916-4925
- DOI
- 10.1039/C8CE00682B
- ISSN
- 1466-8033
- eISSN
- 1466-8033
- Grant note
- DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-FG02-05ER15736; DOI: 10.13039/100007108, name: George Washington University, award: Unassinged
- Language
- English
- Date published
- 2018
- Academic Unit
- Chemistry
- Record Identifier
- 9984216692502771
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