Abstract

Based on density functional theory calculations, polypyridyl ruthenium complexes with phenanthroline polyaromatic based-ligands have been studied in order to understand the effect of the metal fragment on the modulation aromatic character. The changing of the nitrogen position in the ligand, as well as the metal fragment moiety, seems to influence the electronic behavior on the -extended structure and nature of the aromatic character at the ground and excited states. In this framework, structural, electronic, and magnetic based aromaticity indexes were used to understand the aromaticity upon metalation. The aromaticity character of the ligands is highly influenced by the metal fragment, and the aromaticity/antiaromaticity is achieved according to the withdrawing capability of the ligand. The redistribution observed on the aromatic ligand determines their  stacking ability, thus proposing the modulation of the -stacking ability modulated by the electronic nature of the metal fragment.