A detailed study of intermolecular interactions, electronic and vibrational properties of the metal complex bis(uracilato)diammine copper(ii) dihydrate

• Published in: Journal of molecular structure 2018-03, Vol.1155, p.424-433
• Main Authors: Gramajo Feijoo, M., Fernández-Liencres, M.P., Gil, D.M., Gómez, M.I., Ben Altabef, A., Navarro, A., Tuttolomondo, M.E.
• Format: Article
• Language: English
• Subjects: Cu(uracilato-N1)2 (NH3)2] 2H2O complex; DFT; FTIR; Raman; Synthesis
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2017.11.030

Density Functional Theory (DFT) calculations were performed with the aim of investigating the vibrational, electronic and structural properties of [Cu(uracilato-N1)2 (NH3)2]⋅2H2O complex. The IR and Raman spectra were recorded leading to a complete analysis of the normal modes of vibration of the metal complex. A careful study of the intermolecular interactions observed in solid state was performed by using the Hirshfeld surface analysis and their associated 2D fingerprint plots. The results indicated that the crystal packing is stabilized by NH⋯O hydrogen bonds and π-stacking interactions. In addition, CH···π interactions were also observed. Time-dependent density functional theory (TD-DFT) calculations revealed that all the low-lying electronic states correspond to a mixture of intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions. Finally, Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analysis were performed to shed light on the intermolecular interactions in the coordination sphere. [Display omitted] •A complete analysis of the normal modes of vibration of the metal complex has been performed.•TD-DFT investigation gave insights into the optical transition involved in the excitation process.•The hyperconjugative interactions are between nitrogen lone pairs of the ligands and antibonding d-type orbitals.