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.
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