The molecular mechanism of dual emission in terpyridine transition metal complexes--ultrafast investigations of photoinduced dynamics.

Temperature dependent luminescence experiments are combined with femtosecond time-resolved transient absorption spectroscopy to decipher the photoinduced excited-state relaxation pathway in mononuclear Fe, Ru and Os terpyridine complexes bearing a conjugated chromophore within the ligand framework. The herein presented complexes constitute a class of coordination compounds, which overcome the poor emission properties commonly observed for most terpyridine transition metal complexes. As reported earlier, the complexes reveal dual emission at room temperature stemming from ligand centered and metal-to-ligand charge-transfer states. The molecular mechanism of the room temperature dual luminescence is addressed experimentally in this contribution. The experimental results indicate an ultrafast branching reaction within the excited-state manifold upon photoexcitation of the ligand-centered S(1) state. This branching occurs from a "hot" excited state geometry close to the Franck-Condon point of absorption and within ∼100 fs, i.e. the temporal resolution of our experimental setup. The combination of ultrafast differential absorption experiments and temperature-dependent luminescence data allows not only to draw conclusions about the molecular mechanism underlying the observed dual emission but also to construct quantitative Jablonski diagrams and, thereby, to detail the excited-state topology determining the remarkable luminescence properties of the systems at hand.