Effect on the aromaticity of heterocyclic ligands by coordination with ruthenium electron-withdrawing metal centers
Date
Authors
SANHUEZA FRIGOLETT, JUAN MANUEL
DIAZ HARRIS, RAMIRO JOEL
GARCIA SANHUEZA, CAMILO ANDRES
Sanhueza, Luís Manuel
Cortés-Arriagada, Diego
Díaz-Harris, Ramiro
Dreyse, Paulina A.
García, Camilo
González, Iván Alonzo
Loeb, Bárbara L.
DIAZ HARRIS, RAMIRO JOEL
GARCIA SANHUEZA, CAMILO ANDRES
Sanhueza, Luís Manuel
Cortés-Arriagada, Diego
Díaz-Harris, Ramiro
Dreyse, Paulina A.
García, Camilo
González, Iván Alonzo
Loeb, Bárbara L.
Authors
Date
Datos de publicación:
10.1002/qua.26412
Keywords
Aromaticity - Coordination - Heterocyclic Ligands - Ruthenium - ?-stacking - Aromatic Compounds - Aromatization - Density Functional Theory - Electronic Properties - Metals - Ruthenium Compounds - Aromaticity Indices - Coordinated Ligands - Electronic Behaviors - Electronic Distribution - Electronwithdrawing - Extended Structures - Heterocyclic Ligands - Polypyridyl Ruthenium Complexes - Ligands
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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 ?-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 ?-stacking ability; thus, it is proposed that the control of the ?-stacking ability is modulated according to the electronic nature of the ruthenium moiety. © 2020 Elsevier B.V., All rights reserved.
Description
Keywords
Aromaticity , Coordination , Heterocyclic Ligands , Ruthenium , ?-stacking , Aromatic Compounds , Aromatization , Density Functional Theory , Electronic Properties , Metals , Ruthenium Compounds , Aromaticity Indices , Coordinated Ligands , Electronic Behaviors , Electronic Distribution , Electronwithdrawing , Extended Structures , Heterocyclic Ligands , Polypyridyl Ruthenium Complexes , Ligands
Citation
10.1002/qua.26412