Solute-solvent electronic interaction is responsible for initial charge separation in ruthenium complexes [Ru(bpy)3]2+ and [Ru(phen)3]2+

Origin of the initial charge separation in optically-excited Ruthenium(II) tris(bidentate) complexes of intrinsic D-3 symmetry has remained a disputed issue for decades. Here we measure the femtosecond two-photon absorption (2PA) cross section spectra of [Ru(2,2'-bipyridine)3](2) and [Ru(1,10-phenanthroline)(3)](2) in a series of solvents with varying polarity and show that for vertical transitions to the lower-energy (MLCT)-M-1 excited state, the permanent electric dipole moment change is nearly solvent-independent, Delta mu = 5.1-6.3 D and 5.3-5.9 D, respectively. Comparison of experimental results with quantum-chemical calculations of complexes in the gas phase, in a polarizable dielectric continuum and in solute-solvent clusters containing up to 18 explicit solvent molecules indicate that the non-vanishing permanent dipole moment change in the nominally double-degenerate E-symmetry state is caused by the solute-solvent interaction twisting the two constituent dipoles out of their original opposite orientation, with average angles matching the experimental two-photon polarization ratio.