Structural, Spectroscopic, and Computational Analysis of Halogen- and Hydrogen-Bonding Effects within a Series of...

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···O_yl 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 U═O symmetric stretches as a consequence of U═O in-phase and out-of-phase Raman-active stretches. The decrease in the X···O_yl 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.