Photophysical Properties of Ruthenium(II) Polyazaaromatic Compounds: A Theoretical Insight

Quantum-chemical methods are applied to study the nature of the excited states relevant in the photophysical processes (absorption and emission) of a series of polyazaaromatic-ligand-based ruthenium(II) complexes. The electronic and optical properties of the free polyazaaromatic ligands and their corresponding ruthenium(II) complexes are determined on the basis of correlated Hartree-Fock semiempirical approaches. While the emission of complexes containing small-size ligands, such as 1,10-phenanthroline or 2,2′-bipyridine, arises from a manifold of metal-to-ligand charge-transfer triplet states (³MLCTs), an additional ligand-centered triplet state (³L) is identified in the triplet manifold of complexes containing a π-extended ligand such as dipyrido[3,2-a:2′,3′-c]phenazine, tetrapyrido[3,2-a:2′ ,3′-c:3″,2″-h: 2‴,3‴-j]phenazine, and 1,10-phenanthrolino[5,6-b]-1,4,5,8,9,12-hexaazatriphenylene. Recent experimental data are interpreted in light of these theoretical results; namely, the origin for the abnormal solvent- and temperature-dependent emission measured in π-extended Ru complexes is revisited.