Structural, Spectroscopic, and Computational Analysis of Halogen- and Hydrogen-Bonding Effects within a Series of Uranyl Fluorides with 4-Halopyridinium.
Inorg Chem
; 63(5): 2495-2504, 2024 Feb 05.
Article
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| MEDLINE
| ID: mdl-38266166
ABSTRACT
Reported are the syntheses and characterization of five compounds containing one-dimensional uranyl fluoride chains charge balanced by 4-X-pyridinium (X = H, F, Cl, Br, I) cations. Structural analysis reveals molecular assembly via noncovalent interactions in the second coordination sphere with the X···Oyl interaction distances ranging from 2.987(7) to 3.142(3) Å, all of which are less than or close to the sum of the van der Waals radii. These interactions were probed via luminescence and Raman spectroscopy, where the latter indicates slight differences in the UâO symmetric stretches as a consequence of UâO in-phase and out-of-phase Raman-active stretches. The decrease in the X···Oyl sum of the van der Waals overlap between comparable compounds within the series manifests as a red-shifting trend among the Raman symmetric stretches. Computational density functional theory (DFT)-based frequency, electrostatic potential surfaces (ESPs), and natural bonding orbital (NBO) methods support the observed Raman spectroscopic features and provide a comprehensive rationale for assembly.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Año:
2024
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Estados Unidos