Supramolecular structures for determination and identification of the bond lengths in novel uranyl complexes from their infrared spectra

Abstract

Novel dioxouranium (VI) heterochelates with neutral bidentate compounds (Ln) have been synthesized. The ligands and the heterochelates [UO2(Ln)2(O2NO)2] were confirmed and characterized by elemental analysis, 1H NMR, UV.–Vis, IR, mass spectroscopy, X-ray diffraction and thermogravimetric analysis (TGA). IR spectral data suggest that the molecules of the Schiff base are coordinated to the central uranium atom (ON donor). The nitrato groups are coordinated as bidentate ligands. The thermodynamic parameters were calculated using Coats–Redfern and Horowitz–Metzger methods. The ligands (Ln) and their complexes (1–3) showed the υ3 frequency of UO22+ has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ3 of the prepared complexes containing UO22+ were successfully used to calculate the force constant, FUO (1n 10−8N/Å) and the bond length RUO (Å) of the UO bond. A strategy based upon both theoretical and experimental investigations has been adopted. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the UO bond distances from the values of the stretching and interaction force constants. The most probable correlation between UO force constant to UO bond distance were satisfactorily discussed in term of Badger's rule and the equations suggested by Jones and El-Sonbati. The effect of Hammett's constant is also discussed.