Abstract
The reaction of chlorophyll a+ (Chl a+) with either Chl 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 Chl 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 Chl 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 Chl a+-Chl a- reaction in BCN. However, emission from the Chl a+-Chl a- reaction in the other three solvents occurs at 680 nm and corresponds more closely to normal fluorescence from optically excited Chl a. The red-shifted spectra are consistent with the formation of excimers. AC voltammetry of Chl a in BCN provides evidence that Chl a is aggregated in the ground state in this solvent. Chl a reduction shows four waves in BCN and two waves in the other three solvents. Thus, the Chl 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 language | English |
|---|---|
| Pages (from-to) | 6923-6928 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 102 |
| Issue number | 23 |
| Publication status | Published - 1980 |
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Electrochemical production of chlorophyll a and pheophytin a excited states. / Wasielewski, Michael R.; Smith, Rebecca L.; Kostka, Arthur G.
In: Journal of the American Chemical Society, Vol. 102, No. 23, 1980, p. 6923-6928.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Electrochemical production of chlorophyll a and pheophytin a excited states
AU - Wasielewski, Michael R.
AU - Smith, Rebecca L.
AU - Kostka, Arthur G.
PY - 1980
Y1 - 1980
N2 - The reaction of chlorophyll a+ (Chl a+) with either Chl 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 Chl 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 Chl 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 Chl a+-Chl a- reaction in BCN. However, emission from the Chl a+-Chl a- reaction in the other three solvents occurs at 680 nm and corresponds more closely to normal fluorescence from optically excited Chl a. The red-shifted spectra are consistent with the formation of excimers. AC voltammetry of Chl a in BCN provides evidence that Chl a is aggregated in the ground state in this solvent. Chl a reduction shows four waves in BCN and two waves in the other three solvents. Thus, the Chl 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.
AB - The reaction of chlorophyll a+ (Chl a+) with either Chl 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 Chl 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 Chl 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 Chl a+-Chl a- reaction in BCN. However, emission from the Chl a+-Chl a- reaction in the other three solvents occurs at 680 nm and corresponds more closely to normal fluorescence from optically excited Chl a. The red-shifted spectra are consistent with the formation of excimers. AC voltammetry of Chl a in BCN provides evidence that Chl a is aggregated in the ground state in this solvent. Chl a reduction shows four waves in BCN and two waves in the other three solvents. Thus, the Chl 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.
UR - http://www.scopus.com/inward/record.url?scp=0006592914&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0006592914&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0006592914
VL - 102
SP - 6923
EP - 6928
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 23
ER -