Abstract
Ten naturally occurring chlorophylls (a, b, c 2, d) and bacteriochlorophylls (a, b, c, d, e, g) were purified and studied using the optical spectroscopic techniques of both steady state and time-resolved absorption and fluorescence. The studies were carried out at room temperature in nucleophilic solvents in which the central Mg is hexacoordinated. The comprehensive studies of singlet excited state lifetimes show a clear dependency on the structural features of the macrocycle and terminal substituents. The wide-ranging studies of triplet state lifetime demonstrate the existence of an energy gap law for these molecules. The knowledge of the dynamics and the energies of the triplet state that were obtained in other studies allowed us to construct an energy gap law expression that can be used to estimate the triplet state energies of any (B)chlorophyll molecule from its triplet lifetime obtained in a liquid environment.
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Abbreviations
- (B)Chl:
-
(Bacterio)chlorophyll
- ACN:
-
Acetonitrile
- MeOH:
-
Methanol
- THF:
-
Tetrahydrofuran
- OD:
-
Optical density
- T − S:
-
Triplet-minus-singlet
- FTIR:
-
Fourier transform infrared spectroscopy
- HOMO:
-
Highest occupied molecular orbital
- LUMO:
-
Lowest unoccupied molecular orbital
- ISC:
-
Intersystem crossing
- IC:
-
Internal conversion
- ICCD:
-
Intensified charge-coupled device
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Acknowledgments
This research is from the Photosynthetic Antenna Research Center (PARC), an Energy Frontier Research Center funded by the DOE, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC 0001035. We thank Prof. Dewey Holten for helpful discussions.
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Dependency of the triplet state lifetime of BChl c as a function of the number of freeze-pump-thaw cycles (Fig. S1) and digitized datasets (in columns) of absorption (expressed in molar extinction), fluorescence and T-S spectra of all 10 studied molecules.
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Niedzwiedzki, D.M., Blankenship, R.E. Singlet and triplet excited state properties of natural chlorophylls and bacteriochlorophylls. Photosynth Res 106, 227–238 (2010). https://doi.org/10.1007/s11120-010-9598-9
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DOI: https://doi.org/10.1007/s11120-010-9598-9