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 (L n ) have been synthesized. The ligands and the heterochelates [UO 2 (L n ) 2 (O 2 NO) 2 ] were confirmed and characterized by elemental analysis, 1 H 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 (L n ) and their complexes (1–3) showed the υ 3 frequency of UO 2 2+ has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ 3 of the prepared complexes containing UO 2 2+ were successfully used to calculate the force constant, F UO (1n 10 −8 N/A) and the bond length R UO (A) of the U O 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 U O bond distances from the values of the stretching and interaction force constants. The most probable correlation between U O force constant to U O 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.