Delayed Dissociation of Photoexcited Porphyrin Cations in a Storage Ring:  Determination of Triplet Quantum Yields

A technique is described wherein substituent-dependent excited-state properties of gas-phase porphyrins can be accurately quantified. Dissociation lifetimes of photoexcited porphyrin cations were measured in an electrostatic ion storage ring. From these data, upper limits for the triplet quantum yie...

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Published inThe journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 109; no. 17; pp. 3875 - 3879
Main Authors Nielsen, Christian B, Forster, James S, Ogilby, Peter R, Nielsen, Steen Brøndsted
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 05.05.2005
Subjects
Cations
Chemistry, Physical - methods
Helium - chemistry
Ions
Light
Models, Chemical
Oxygen - chemistry
Photochemistry - methods
Photons
Porphyrins - chemistry
Quantum Theory
Singlet Oxygen - chemistry
Spectrometry, Mass, Electrospray Ionization
Time Factors
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Summary:A technique is described wherein substituent-dependent excited-state properties of gas-phase porphyrins can be accurately quantified. Dissociation lifetimes of photoexcited porphyrin cations were measured in an electrostatic ion storage ring. From these data, upper limits for the triplet quantum yield of the following protonated porphyrins were obtained:  protoporphyrin IX (0.63 ± 0.04), tetraphenylporphyrin (0.73 ± 0.03), tetra(p-methylphenyl)porphyrin (0.75 ± 0.03), and tetra(p-cyanophenyl)porphyrin (0.71 ± 0.03). The values compare well with those for porphyrins in solution.
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ISSN:1089-5639
1520-5215
DOI:10.1021/jp050464p