Two-pump-one-probe femtosecond studies of Ni(II) porphyrins excited states.

Dual excited states of nickel(II) meso-tetra(4-sulfonatophenyl)porphyrin (NiTPPS) and nickel(II) meso-tetraphenylporphyrin (NiTPP) have been investigated by two-pump-one-probe transient absorption spectrometry. By dual excited states, we mean molecular entities that have absorbed two photons to generate molecular states with electronic excitation in two distinct regions of metalloporphyrin. Two successive pulses of 400 and 550 nm were used for excitation. The first pulse (400 nm) produced an S2 state of the porphyrin pi-system, which deactivated to give rise to an S1 state and subsequently produce a metal-centered (d,d) state. The second (550 nm) pulse selectively targeted an S0 --> S1 transition of those molecules having an excited metal center and was delivered to the sample approximately 40 ps after the first excitation event. At this time, the ground state of the tetrapyrrole pi-system was already regenerated and the excitation was localized at the metal center. The kinetic profiles of the NiTPPS transients in DMSO revealed biexponential decays with time constants of 0.6 and 4 ps. Photoexcitation of NiTPP in toluene and NiTPPS in water resulted in similar behavior. A mechanism for the Ni(II) porphyrin dual excited state deactivation involving the formation of an intramolecular charge transfer state has been proposed.