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Molecular and electronic structures, bonding analysis, and UV–Vis spectra predictions of quinolino[3,2-b]benzodiazepine and quinolino[3,2-b]benzoxazepine metal transition M(L)2Cl2 and M(L)Cl2 complexes

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Abstract

Density functional theory (DFT) calculations were carried out on ML2Cl2 (M = Co, Ni) and M’LCl2 (M’= Zn, Cd) and L=(BDQ) quinolino[3,2-b]benzodiazepine or L = (BDO) = quinolino[3,2-b]benzoxazepine) transition metal complexes. The geometry optimizations and frequency calculations of the aforementioned complexes were performed at the Becke, 3-parameter, Lee–Yang–Parr/triple zeta polarization (B3LYP/TZP) level, followed by the partitioning of the interaction energies using the energy decomposition analysis scheme (EDA) to assess the interaction strength in function of L ligand and the nature of the metal. Indeed, the total bonding energies are more significant for Zn(II) cation in the presence of (QBD) ligand than those of the Cd(II) one and (QBO). The findings show that the electrostatic interaction energy is the most important contributing by two third into the total interaction energy of each of the complex systems. Calculations and analyses were performed by means of the natural bond orbital analyses (NBO) giving rise to significant natural population of the M(II) cations. As concerns of the structures corresponding to odd electron counts, the unpaired electrons are chiefly localized on the metal center with regard to the spin density values. UV–Vis spectra are mainly π→π* electronic transitions corresponding to intra-ligand charge transfers (ILCT) but showed weak influence of the introduction of the MCl2 metallic fragment.

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Funding

The authors are grateful to the Algerian MESRS (Ministère de l’Enseignement Supérieur et de la Recherche Scientifique) and the Algerian DGRSDT (Direction Générale de la Recherche Scientifique et du Développement Technologique) for the financial support.

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  1. Université de Tebessa, 12000, Tebessa, Algeria

    Yasmina Hafsi

  2. Laboratoire de Chimie Appliquée Et Technologie Des Matériax, Université Larbi Ben M’hidi Oum, 04000, El Bouaghi, Oum El Bouaghi, Algeria

    Yasmina Hafsi, Sabri Mecheri & Bachir Zouchoune

  3. Unité de Recherche de Chimie de L’Environnement Et Moléculaire Structurale, Université Constantine 1 (Mentouri), 25000, Constantine, Algeria

    Bachir Zouchoune

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Yasmina Hafsi: execution of DFT calculations, results collection, and conceptualization. Sabri Mecheri: writing original draft. Bachir Zouchoune: conceptualization, manuscript writing, and validation.

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Hafsi, Y., Mecheri, S. & Zouchoune, B. Molecular and electronic structures, bonding analysis, and UV–Vis spectra predictions of quinolino[3,2-b]benzodiazepine and quinolino[3,2-b]benzoxazepine metal transition M(L)2Cl2 and M(L)Cl2 complexes. Struct Chem 34, 2051–2064 (2023). https://doi.org/10.1007/s11224-023-02145-9

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