Rights statement: © Royal Society of Chemistry 2018
Accepted author manuscript, 1.1 MB, PDF document
Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License
Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - Probing Hydrogen and Halogen-Oxo Interactions in Uranyl Coordination Polymers
T2 - A Combined Crystallographic and Computational Study
AU - Carter, Korey
AU - Kalaj, Mark
AU - Kerridge, Andrew
AU - Cahill, Christopher
PY - 2018/9/14
Y1 - 2018/9/14
N2 - 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.
AB - 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.
U2 - 10.1039/C8CE00682B
DO - 10.1039/C8CE00682B
M3 - Journal article
VL - 20
SP - 4916
EP - 4925
JO - CrystEngComm
JF - CrystEngComm
SN - 1466-8033
IS - 34
ER -