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Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Structural, spectroscopic, and computational evaluations of cation-cation and halogen bonding interactions in heterometallic uranyl hybrid materials
AU - Carter, K.P.
AU - Kalaj, M.
AU - McNeil, S.
AU - Kerridge, A.
AU - Schofield, M.H.
AU - Ridenour, J.A.
AU - Cahill, C.L.
PY - 2021/3/7
Y1 - 2021/3/7
N2 - Harnessing the nominally terminal oxo atoms of the linear uranyl (UO22+) cation represents a frontier within the field of f-element hybrid materials. Here we outline a route for systematically accessing uranyl oxo atoms via judicious pairing with Ag+ cations or iodobenzoates, and describe the syntheses and crystal structures of four new heterometallic compounds containing Ag+ cations, the UO22+ cation, and o- (1), m- (2), p-iodo- (3), and 2,5-diiodo- (4) carboxylate ligands. Vibrational and luminescence spectroscopic properties for all four compounds are reported, as are computational findings from quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analyses. Single crystal X-ray diffraction analysis of compounds 1-4 shows that the nominally terminal uranyl oxo atoms are engaged in either covalent UO2-Ag cation-cation interactions (1 and 3) or non-covalent assembly via halogen bonding interactions (2 and 4). Raman, infrared (IR), and luminescence spectra of 1-4 are redshifted with respect to the free uranyl cation indicating that both halogen-oxo and cation-cation interactions weaken the UO bond, and in the case of 3 we note a rare example of activation of the uranyl asymmetric stretch (ν3) in the Raman spectra, likely due to the Ag-oxo cation-cation interaction lowering the symmetry of the uranyl cation. Quantum chemical calculations and QTAIM analysis highlight a quantitative difference between halogen bonds and cation-cation interactions, with the latter shown to significantly decrease uranyl bond orders and electron density at bond critical points.
AB - Harnessing the nominally terminal oxo atoms of the linear uranyl (UO22+) cation represents a frontier within the field of f-element hybrid materials. Here we outline a route for systematically accessing uranyl oxo atoms via judicious pairing with Ag+ cations or iodobenzoates, and describe the syntheses and crystal structures of four new heterometallic compounds containing Ag+ cations, the UO22+ cation, and o- (1), m- (2), p-iodo- (3), and 2,5-diiodo- (4) carboxylate ligands. Vibrational and luminescence spectroscopic properties for all four compounds are reported, as are computational findings from quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analyses. Single crystal X-ray diffraction analysis of compounds 1-4 shows that the nominally terminal uranyl oxo atoms are engaged in either covalent UO2-Ag cation-cation interactions (1 and 3) or non-covalent assembly via halogen bonding interactions (2 and 4). Raman, infrared (IR), and luminescence spectra of 1-4 are redshifted with respect to the free uranyl cation indicating that both halogen-oxo and cation-cation interactions weaken the UO bond, and in the case of 3 we note a rare example of activation of the uranyl asymmetric stretch (ν3) in the Raman spectra, likely due to the Ag-oxo cation-cation interaction lowering the symmetry of the uranyl cation. Quantum chemical calculations and QTAIM analysis highlight a quantitative difference between halogen bonds and cation-cation interactions, with the latter shown to significantly decrease uranyl bond orders and electron density at bond critical points.
KW - Atoms
KW - Carboxylation
KW - Chemical analysis
KW - Chemical bonds
KW - Computation theory
KW - Crystal atomic structure
KW - Halogen compounds
KW - Hybrid materials
KW - Luminescence
KW - Metallic compounds
KW - Oxide minerals
KW - Quantum chemistry
KW - Quantum theory
KW - Silver metallography
KW - Single crystals
KW - Uranium dioxide
KW - X ray powder diffraction
KW - Cation-cation interactions
KW - Computational evaluation
KW - Heterometallic compounds
KW - Luminescence spectrum
KW - Quantum chemical calculations
KW - Quantum Theory of Atoms in Molecules
KW - Single crystal X-ray diffraction analysis
KW - Spectroscopic property
KW - Positive ions
U2 - 10.1039/d0qi01319f
DO - 10.1039/d0qi01319f
M3 - Journal article
VL - 8
SP - 1128
EP - 1141
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
IS - 5
ER -