Nickel porphyrin photophysics and photochemistry. A picosecond investigation of ligand binding and release in the excited state

Dongho Kim, Christine Kirmaier, Dewey Holten

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The photophysical behavior and some photochemical processes for nickel (II) porphyrins have been examined with picosecond transient absorption techniques. Detailed results are reported for Ni-octaethylporphyrin (NiOEP) and Ni-protoporphyrin IX dimethylester (NiPPDME) in toluene, pyridine and piperidine. Excitation flashes at six wavelengths between 355 and 532 nm have been employed. In toluene, rapid (≤ 15 ps) radiationless decay occurs via several pathways to the low-lying 3B1g excited state. In the basic solvents pyridine and piperidine, excited states with nickel 1A1g (dz2) character have a tendency to release ligands bound to the metal. Excited states with nickel 1B1g or 3B1g (dz2, dx2-y2) character on the other hand, have an affinity for basic ligands, which rapidly bind to the metal. The competition between radiationless decay, ligand binding, and ligand release depends on the nickel porphyrin, solvent, and excitation wavelength. A set of "rules" has been developed that gives a consistent view of all of our results and those of previous investigators. These results may be helpful in understanding photoprocesses in other transition-metal porphyrins, including hemes, which have particular biological significance.

Original languageEnglish
Pages (from-to)305-322
Number of pages18
JournalChemical Physics
Issue number3
Publication statusPublished - 1983 Mar 15


All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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