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Excited state properties of chlorophyll f in organic solvents at ambient and cryogenic temperatures

Abstract

Chlorophyll f is a photosynthetic pigment that was discovered in 2010. In this study, we present investigations on spectral and dynamic characteristics of singlet-excited and triplet states of Chl f with the application of ultrafast time-resolved absorption and fluorescence spectroscopies. The pigment was studied at room temperature in two organic solvents: pyridine and diethyl ether that have different characters of coordination of the chlorophyll magnesium (Mg) atom (hexa- and penta-coordination, respectively). Cryogenic measurements (77 K) were performed in 2-methyltetrahydrofuran (hexa-coordination). The singlet-excited state lifetime was measured to be 5.6 ns at room temperature regardless of Mg coordination and 8.1 ns at 77 K. The fluorescence quantum yield of Chl f was also determined in pyridine to be 0.16. The triplet state lifetime was studied in detail in pyridine at room temperature, and the inherent lifetime was estimated to ~150 μs. Selective measurements at 77 K demonstrated that the metastability of the triplet state greatly enhances, and its lifetime increases by a factor of more than three.

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Abbreviations

2-MTHF:

2-Methyl tetrahydrofuran

CCD:

Charge couple device

Chl:

Chlorophyll

DE:

Diethyl ether

EADS:

Evolution-associated difference spectra

ESA:

Excited state absorption

FWHM:

Full width at half maximum

HOMO:

Highest occupied molecular orbital

ICP-MS:

Inductively coupled plasma-mass spectrometry

LUMO:

Lowest unoccupied molecular orbital

OPO:

Optical parametric oscillator

Pyr:

Pyridine

RT:

Room temperature

TA:

Transient absorption

TRF:

Time-resolved fluorescence

T-S:

Triplet-minus-singlet

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Acknowledgments

This research was performed in the Photosynthetic Antenna Research Center (PARC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC 0001035 to R.E.B. M.C. is an Australian Future Fellow and thanks Australia Research Council for financial support.

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Correspondence to Dariusz M. Niedzwiedzki.

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Niedzwiedzki, D.M., Liu, H., Chen, M. et al. Excited state properties of chlorophyll f in organic solvents at ambient and cryogenic temperatures. Photosynth Res 121, 25–34 (2014). https://doi.org/10.1007/s11120-014-9981-z

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  • DOI: https://doi.org/10.1007/s11120-014-9981-z

Keywords

  • Chlorophyll f
  • Transient absorption
  • Singlet-excited state
  • Triplet state
  • Time-resolved fluorescence
  • Halomicronemona hongdechloris