New Twist on the Light-Switch Effect: Controlling the Fate of Excited States with pH in a 4-Hydroxy-thiazol-extended Ruthenium(II) Dppz Complex.

We present a pH-dependent study of the excited state dynamics of a novel Ru complex bearing a 4-hydroxy thiazol-substituted dppz (dipyridophenazine) ligand ( RuTzOH ) and its deprotonated form ( RuTzO - ). We combine steady-state and time-resolved absorption and emission spectroscopy with electrochemical investigations to characterize the excited state relaxation, which upon photoexcitation at 400 nm is determined by a multitude of initially populated MLCT states for both complexes. Subsequently, for RuTzOH , two long-lived excited states are populated, leading to dual emission from the complexes, a feature that vanishes upon deprotonation. Upon deprotonation, the electron density on the dppz moiety increases significantly, leading to rapid energy populating ligand-centered states and thus deactivating the initially excited MLCT states.