Electrochemical Production of Chlorophyll a and Pheophytin a Excited States

Michael R. Wasielewski*, Rebecca L. Smith, Arthur G. Kostka

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

33 Scopus citations


The reaction of chlorophyll a+ (Chi a+) with either Chi a- or pheophytin a- (Pheo a-) in addition to the reaction of Pheo a+ with Pheo a- was studied in butyronitrile (BCN), BCN-1% THF, THF, and DMF. The electrochemically produced radical ion pairs Chi a+-Chl a- and Pheo a+-Pheo a- react in each solvent to produce a 10-7- 10-6 yield of luminescent states on the basis of the initial number of radical pairs. The Chi a+-Pheo a- reaction produces no observable luminescence in any of the solvents examined. The luminescence maximum for the Pheo a+-Pheo a” reaction occurs at 730 nm in each solvent and is strongly red-shifted relative to the fluorescence maxima for optically excited Pheo a in these solvents. A similar result is obtained for the Chi a+-Chl a- reaction in BCN. However, emission from the Chi a+-Chl a- reaction in the other three solvents occurs at 680 nm and corresponds more closely to normal fluorescence from optically excited Chi a. The red-shifted spectra are consistent with the formation of excimers. AC voltammetry of Chi a in BCN provides evidence that Chi a is aggregated in the ground state in this solvent. Chi a reduction shows four waves in BCN and two waves in the other three solvents. Thus, the Chi a+-Chl a- reaction in BCN does not form a true excimer, whereas the Pheo a+-Pheo a- reactions in each solvent do. The luminescence efficiencies of these charge-transfer neutralization reactions are discussed in terms of the geometric constraints on electron-transfer reactions in photosynthetic reaction centers.

Original languageEnglish (US)
Pages (from-to)6923-6928
Number of pages6
JournalJournal of the American Chemical Society
Issue number23
StatePublished - Sep 1980

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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