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Effect on the aromaticity of heterocyclic ligands by coordination with ruthenium electron-withdrawing metal centers |
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| Authors: | Luis Sanhueza Diego Cortés-Arriagada Ramiro Díaz Paulina Dreyse Camilo García Iván A Gonzalez Bárbara Loeb |
| Institution: | 1. Departamento de Ciencias Biológicas y Químicas, Facultad de Recursos Naturales, Universidad Católica de Temuco, Temuco, Chile;2. Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, San Joaquín, Chile;3. Departamento de Ciencias Biológicas y Químicas, Facultad de Recursos Naturales, Universidad Católica de Temuco, Temuco, Chile
Contribution: Methodology;4. Departamento de Química, Universidad Técnica Federico Santa María, Valparaíso, Chile;5. Departamento de Ciencias Biológicas y Químicas, Facultad de Recursos Naturales, Universidad Católica de Temuco, Temuco, Chile Núcleo de Investigación en Bioproductos y Materiales Avanzados (BioMA), Universidad Católica de Temuco, Av. Rudecindo Ortega 02950, Temuco, Chile Contribution: Writing - original draft;6. Instituto de Investigación e Innovación en Salud, Facultad de Ciencias de la Salud, Universidad Central de Chile, Santiago, Chile Contribution: Formal analysis;7. Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, Chile Contribution: Writing - review & editing |
| Abstract: | Density functional theory calculations of polypyridyl ruthenium complexes with polyaromatic ligands have been performed to understand the metal fragment effect on the modulation of their electronic properties and the influence on the aromatic character. The change of positions of the nitrogen atoms in the ligand structure, as well as the metal moiety, seems to influence the electronic behavior of the π-extended structure and the aromatic character of the complexes at both the ground and excited states. In this framework, structural, electronic, and magnetic-based aromaticity indices were used to understand the aromaticity of the free and coordinated ligands. The aromaticity character of the ligands is highly influenced by the metal fragment, and the aromaticity/antiaromaticity is achieved according to both the electron-withdrawing capability of the ligand and the metal fragment. The electronic distribution observed on the aromatic ligand determines their π-stacking ability; thus, it is proposed that the control of the π-stacking ability is modulated according to the electronic nature of the ruthenium moiety. |
| Keywords: | aromaticity coordination heterocyclic ligands ruthenium π-stacking |