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Singlet and triplet excited state properties of natural chlorophylls and bacteriochlorophylls

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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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Authors and Affiliations

  1. Departments of Biology and Chemistry, Washington University in St. Louis, St. Louis, MO, 63130-4899, USA

    Dariusz M. Niedzwiedzki & Robert E. Blankenship

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  1. Dariusz M. Niedzwiedzki
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  2. Robert E. Blankenship
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Correspondence to Robert E. Blankenship.

Electronic supplementary material

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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