Ultrafast energy transfer from a carotenoid to a chlorin in a simple artificial photosynthetic antenna

Alisdair N. Macpherson, Paul A. Liddell, Darius Kuciauskas, Dereck Tatman, Tomas Gillbro, John Devens Gust, Thomas A Moore, Ana L Moore

Research output: Contribution to journalArticle

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Abstract

A model photosynthetic antenna system consisting of a carotenoid moiety covalently linked to a purpurin has been prepared to study singlet-singlet energy transfer from a carotenoid to a cyclic tetrapyrrole. Ultrafast fluorescence upconversion measurements of the carotenopurpurin dyad and an unlinked reference carotenoid demonstrate that the fluorescent S2 excited state of the carotenoid model has a lifetime of 150 ± 3 fs, whereas the corresponding excited state of the carotenoid in the carotenopurpurin dyad is quenched to 40 ± 3 fs. This quenching is assigned to energy transfer from the S2 state to the purpurin with a 73 ± 6% efficiency, which is in accord with the 67 ± 4% quantum yield obtained by steady-state fluorescence excitation measurements. Concomitant with the decay of the carotenoid S2 excited state, a single-exponential rise of the excited S1 state of the purpurin moiety was observed at 699 nm with a time constant of 64 fs. However, the decay of the fluorescence anisotropy was faster at this wavelength (40 fs) and isotropic rise times as short as 44 fs were determined at other emission wavelengths. The lifetime of the S1 state of the carotenoid (7.8 ps) was the same in both the carotenoid model and the dyad. Taken together, these results unequivocally demonstrate that the S2 state of the carotenoid moiety is the sole donor state in this efficient singlet-singlet energy transfer process. The simple dyad described in this work mimics the ultrafast energy transfer kinetics found in certain naturally occurring pigment protein complexes and is thus able to reproduce the high electronic coupling needed for efficient energy transfer from an extremely short-lived energy donor state.

Original languageEnglish
Pages (from-to)9424-9433
Number of pages10
JournalJournal of Physical Chemistry B
Volume106
Issue number36
DOIs
Publication statusPublished - Sep 12 2002

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carotenoids
Carotenoids
Energy transfer
antennas
energy transfer
Antennas
Excited states
Fluorescence
fluorescence
excitation
Tetrapyrroles
chlorin
life (durability)
Wavelength
decay
Quantum yield
pigments
Pigments
wavelengths
time constant

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ultrafast energy transfer from a carotenoid to a chlorin in a simple artificial photosynthetic antenna. / Macpherson, Alisdair N.; Liddell, Paul A.; Kuciauskas, Darius; Tatman, Dereck; Gillbro, Tomas; Gust, John Devens; Moore, Thomas A; Moore, Ana L.

In: Journal of Physical Chemistry B, Vol. 106, No. 36, 12.09.2002, p. 9424-9433.

Research output: Contribution to journalArticle

Macpherson, Alisdair N. ; Liddell, Paul A. ; Kuciauskas, Darius ; Tatman, Dereck ; Gillbro, Tomas ; Gust, John Devens ; Moore, Thomas A ; Moore, Ana L. / Ultrafast energy transfer from a carotenoid to a chlorin in a simple artificial photosynthetic antenna. In: Journal of Physical Chemistry B. 2002 ; Vol. 106, No. 36. pp. 9424-9433.
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