Porphyrin-Sensitized Generation of Singlet Molecular Oxygen: Comparison of Steady-State and Time-Resolved Methods

1995 ◽  
Vol 99 (24) ◽  
pp. 9825-9830 ◽  
Author(s):  
Charles Tanielian ◽  
Christian Wolff
Keyword(s):  
Steady State ◽  
Molecular Oxygen ◽  
Singlet Molecular Oxygen ◽  
Time Resolved

Photophysics of novel 22π porphyrinoids

2012 ◽  
Vol 16 (05n06) ◽  
pp. 499-507 ◽  
Author(s):  
Daniel O. Mártire ◽  
Sigrid Russell ◽  
Hans-Jürgen Dietrich ◽  
Carlos J. Cobos ◽  
Silvia E. Braslavsky
Keyword(s):  
Triplet State ◽  
Molecular Oxygen ◽  
Photophysical Properties ◽  
Intersystem Crossing ◽  
Quenching Rate ◽  
Triplet Energy ◽  
Singlet Molecular Oxygen ◽  
Time Resolved ◽  
Quenching Rate Constant ◽  
New Compounds

The photophysical properties of toluene solutions of two new 22π expanded porphycene compounds were measured using a combination of various steady-state and time-resolved techniques. The determined triplet energy (E T = 109 ± 3) kJ.mol-1, coincident with the calculated E T = (96.0 ± 10) kJ.mol-1, of both red absorbing compounds is higher than the energy required to excite ground state molecular oxygen to singlet molecular oxygen. However, the intersystem crossing yield is very low (ca. 10-2), which makes these compounds poor photosensitizers. The triplet state yield of the two expanded 22π porphyrinoid compounds is much lower than that of the parent porphycene, whereas their fluorescence is as high (ca. 30%) as the value for porphycene. The slower than diffusional quenching rate constant of a porphycene triplet state by the two new compounds reflects a steric hindering factor of the exothermic energy transfer.

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