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  4. Ultrafast Broadband Fluorescence Up-conversion Study of the Electronic Relaxation of Metalloporphyrins
 
research article

Ultrafast Broadband Fluorescence Up-conversion Study of the Electronic Relaxation of Metalloporphyrins

Bram, Olivier  
•
Cannizzo, Andrea  
•
Chergui, Majed  
February 21, 2019
The Journal of Physical Chemistry A

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 relaxation is significantly slowed down and is multiexponential. We argue that because of a lower density of states in the region of the Soret band, compared to ZnOEP, the relaxation time becomes much longer. Finally, the role of metal orbitals is apparent in the relaxation of the Q-state, which is found to be much faster in the case of open-shell metals compared to closed-shell ones, hinting to an electron transfer from the porphyrin to the metal.

  • Details
  • Metrics
Type
research article
DOI
10.1021/acs.jpca.9b00007
Web of Science ID

WOS:000459836600021

Author(s)
Bram, Olivier  
Cannizzo, Andrea  
Chergui, Majed  
Date Issued

2019-02-21

Publisher

AMER CHEMICAL SOC

Published in
The Journal of Physical Chemistry A
Volume

123

Issue

7

Start page

1461

End page

1468

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

soret-excited tetrapyrroles

•

femtosecond fluorescence

•

free-base

•

optical-properties

•

condensed-phase

•

state dynamics

•

porphyrins

•

photophysics

•

zinc

•

energy

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSU  
Available on Infoscience
March 13, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/155552
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