Journal
CHEMICAL PHYSICS
Volume 280, Issue 1-2, Pages 177-190Publisher
ELSEVIER
DOI: 10.1016/S0301-0104(02)00485-8
Keywords
porphyrins; radiationless transitions; tunnel-effect theory; heavy-atom effect
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The photophysics of halogenated and metallated tetrakisphenylporphyrins is investigated using single-photon counting, photoacoustic calorimetry and luminescence techniques. The radiationless transition rates in these and related molecules are interpreted with a quantum-mechanical tunnelling model modified to include the effect of spin-orbit coupling in the intersystem crossing rates. It is shown that tetrakisphenylporphyrins with halogens in the ortho positions have long-lived triplet states that are formed in high yields. (C) 2002 Elsevier Science B.V. All rights reserved.
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