Ultrafast Broadband Fluorescence Up-conversion Study of the Electronic Relaxation of Metalloporphyrins
- Bram, Olivier
- Cannizzo, Andrea
- Chergui, Majed
DOIAbstract
We present a systematic study of the ultrafast fluorescence with broadband detection and similar to 110 fs resolution of 5,10,15,20-tetraphenylporphin (TPP) and 2,3,7,8,12,13,17,18-oc-taethylporphin (OEP), with open 3d-shell metals. We also revisit the cases of the closed-shell ZnTPP and ZnOEP systems. We find that in all cases, the relaxation from the Soret (B)-state to the Q-states (S-1) occurs on ultrafast time scales of <50-100 fs, regardless of the metal, its oxidation state, and the peripheral groups of the macrocycle. The analogy with free base TPP and OEP leads us to conclude that the B-Q relaxation involves only the porphyrin states. ZnTPP is an outlier compared to the entire set of investigated systems, in the sense that the B-Q r...
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