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The molecular structure, the Natural Bond orbital (NBO) and the Time Dependent-DFT of both isomers cis or γ-Cl and trans or δ-Cl of RuCl2(L)2, where L stands respectively for 2-phenylazopyridine (Azpy), 2,4-dimethyl-6-[phenylazo]pyridine (Dazpy), 2-[(3,5-dimethylphenyl)azopyridine] (Mazpy) and 2-pyridylazonaphtol (Nazpy) were calculated with DFT method at B3LYP/LANL2DZ level. The prediction of the frontier orbitals (Highest Occupied Molecular Orbital or HOMO and Lowest Unoccupied Molecular Orbital or LUMO) shows that the most active complexes suitable for electronic reactions are admitted to be the trans isomers. Moreover, δ-RuCl2 (Azpy)2 is discovered to react more actively as photo-sensitizer since its energy gap is the minimum. Besides, electronic structures of all complexes through NBO calculation indicate that Ru-N bonds are made of delocalization of occupancies from lone pair orbital of N atoms to the ruthenium. Moreover, Ru was assumed to have almost the same charge regardless the structure of the azopyridine ligands in the complex indicating that the ligands provide only a steric effect that is responsible for the ruthenium’s selectivity. Concerning the transition state, NBO analysis also highlights that the transition LP(Ru) π*(N1-N2) does correspond to t2g π*(L). This transition is assumed to correspond to Metal to Ligand Charge Transfer (MLCT) that is responsible for the photo-sensitiveness of the metallic complex. Besides, TDDFT calculation of complexes showed that δ-RuCl2(Nazpy)2 displays the largest band during the absorption. For that reason, it is admitted to be the best photosensitizer due to a large system of conjugation provided by Nazpy ligand.

NBO Population Analysis and Electronic Calculation of Four Azopyridine Ruthenium Complexes by DFT Method