Lamb, Ryan M.
; Smith, Laura E.
; Natan, Adi
; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Detailed understanding of the photophysical properties of metalloporphyrins is key to rationally exploiting them in a variety of applications ranging from photocatalysis to opto-magnetics. Previous studies of the ferric-tetraphenylporphyrin chloride have provided contradictory descriptions of the excited state evolution. Optical transient-absorption suggested initial formation of a ΟΟ* excited state, followed by ligand-to-metal charge-transfer (LMCT) from the porphyrin ring and then decay on the βΌ2 ps time scale to a metal-centered excited state that had a lifetime of βΌ15 ps. In contrast, femtosecond extreme ultraviolet transient-absorption at the Fe M
2,3-edge, while agreeing on the initial formation of an LMCT state, found
more » evidence that this decayed in βΌ2 ps to the ground state. Here, we have used K-edge transient X-ray absorption and X-ray emission, together with time-resolved X-ray solution scattering to explore this system. Based on these data, we propose a new model, consistent with both the earlier and the current data, in which photoexcited FeTPPCl evolves through three different states on the LMCT manifold, with the βΌ2 ps decay now seen to involve a branching between return to the ground state (βΌ70%) and formation of a long-lived LMCT state (βΌ30%).« less