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Efficient non-radiative deactivation and conformational flexibility of meso-diaryloctaalkylporphyrins in the excited triplet state

Joakim Andréasson (Institutionen för fysikalisk kemi) ; Hanna Zetterqvist (Institutionen för fysikalisk kemi) ; Johan Kajanus (Institutionen för kemi och biovetenskap, Organisk kemi) ; Jerker Mårtensson (Institutionen för kemi och biovetenskap, Organisk kemi) ; Bo Albinsson (Institutionen för fysikalisk kemi)
Journal of Physical Chemistry A (1089-5639). Vol. 104 (2000), 41, p. 9307-9314.
[Artikel, refereegranskad vetenskaplig]

The excited triplet state deactivation of zinc(II) meso-diaryloctaalkylporphyrins (ZnDAOAP) has been studied over a wide temperature range using transient triplet-triplet absorption spectroscopy together with steady-state and time-resolved phosphorescence techniques, The results from transient absorption measurements show that the depopulation of the initially formed triplet state (T-1A state) is unusually fast at temperatures above 150 K. The efficiency of the deactivation originates from a spin allowed transition to a second tripler state (T-1B state), The transformation process T-1A-->T-1B is therefore the dominating deactivation channel of the T-1A state in this temperature range, and direct intersystem crossing T-1A-->S-0 makes negligible contribution. The subsequent ground-state recovery T-1B-->S-0 is also very efficient in comparison to many other porphyrins. Due to the substantial activation energy found for the transformation process, it most likely involves a conformational distortion of the porphyrin macrocycle. At low temperature, however, the relaxation of the T-1A State occurs by direct intersystem crossing to the ground state.



Denna post skapades 2007-01-30. Senast ändrad 2017-10-03.
CPL Pubid: 26063

 

Institutioner (Chalmers)

Institutionen för fysikalisk kemi (1900-2003)
Institutionen för kemi och biovetenskap, Organisk kemi (1900-2004)

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Chalmers infrastruktur