Photoinduced Ligand Exchange Dynamics of a Polypyridyl Ruthenium Complex in Aqueous Solution

The understanding of photoinduced ligand exchange mechanisms in polypyridyl ruthenium(II) complexes operating aqueous solution is crucial importance to rationalize their photoreactivity. Herein, we demonstrate that a synergetic use ab initio molecular dynamics simulations and static calculations, both conducted at the DFT level, can provide full photosubstitution monodentate by solvent water molecule archetypal ruthenium explicit water. show loss generates an unreactive 16-electron species hitherto undescribed pentacoordinated triplet excited state converts, via easily accessible crossing point, reactive singlet ground state, which combines with yield experimentally observed aqua complex less than 10 ps. This work paves way for rational design novel photoactive metal relevant biological applications.