Fig. 1.
The excited states of RuPZn have oppositely oriented electric dipole moments. (A) The electronic absorption spectrum of RuPZn displays distinct absorption manifolds into S1 (red), S2 (green), and S3 (blue) excited states. Arrows demark the excitation (pump) wavelengths of RuPZn used in the pump–probe experiments of this report, which are also the two-photon-resonant wavelengths of the dynamic hyperpolarizability (βλ) experiments (boxes) in B. (B) βλ-spectrum (gold) of RuPZn determined from experimentally measured values (boxes) (6, 11, 12). See SI Appendix for more details. (C) One-electron oxidation and reduction potentials (vs. standard calomel electrode) of RuPZn in acetonitrile solvent. Colored arrows show that the one-electron oxidations and reductions track with the ground- to excited-state energies. These one-electron transitions qualitatively describe the CT character of the corresponding excited states, as well as the electronic polarizations described in B.