Light harvesting and photoprotective functions of carotenoids in compact artificial photosynthetic antenna designs

Gerdenis Kodis, Christian Herrero, Rodrigo Palacios, Ernesto Mariño-Ochoa, Stephanie Gould, Linda De La Garza, Rienk Van Grondelle, John Devens Gust, Thomas A Moore, Ana L Moore, John T M Kennis

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Abstract

Artificial light-harvesting constructs were synthesized by covalently linking two carotenoids to the central silicon atom of a phthalocyanine (Pc) derivative. Triad 1 binds two carotenoids having nine conjugated double bonds, whereas triad 2 binds two carotenoids having 10 carbon-carbon double bonds in conjugation. Fluorescence excitation experiments indicated that, in triad 1 dissolved in n-hexane, the carotenoid to Pc singlet energy transfer efficiency is ca. 92%, whereas in triad 2, it is 30%. Results from ultrafast laser spectroscopy indicate that upon population of the optically allowed S2 state of the carotenoid the optically forbidden states S1 and S* are rapidly generated in both triad 1 and triad 2. In triad 1, S2, S1 and S* all contribute singlet electronic energy to Pc. In triad 2, singlet electronic energy transfer to Pc occurs primarily from the optically allowed S2 state with little energy transfer to Pc via the S1 state, and there is no evidence for energy transfer via S*. Instead, in triad 2, we find a multiphased quenching of the Pc singlet excited state on the picosecond and nanosecond time scales. Upon intersystem crossing from the singlet excited state of Pc to the triplet state in triad 1, triplet-triplet energy transfer to either of the carotenoids takes place on a time scale significantly shorter than 5 ns. When dissolved in polar solvents, triads 1 and 2 exhibit light-induced electron transfer from either of the carotenoid moieties to the excited singlet Pc species with a time constant of about 2 ps. Charge recombination to the singlet ground state occurs in 10 ps in triad 1 and 17 ps in triad 2.

Original languageEnglish
Pages (from-to)414-425
Number of pages12
JournalJournal of Physical Chemistry B
Volume108
Issue number1
Publication statusPublished - Jan 8 2004

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carotenoids
antenna design
Carotenoids
Antennas
Energy transfer
energy transfer
Excited states
Carbon
excitation
Ultrafast lasers
Laser spectroscopy
carbon
phthalocyanine
Hexane
conjugation
laser spectroscopy
electronics
Silicon
Ground state
atomic energy levels

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Kodis, G., Herrero, C., Palacios, R., Mariño-Ochoa, E., Gould, S., De La Garza, L., ... Kennis, J. T. M. (2004). Light harvesting and photoprotective functions of carotenoids in compact artificial photosynthetic antenna designs. Journal of Physical Chemistry B, 108(1), 414-425.

Light harvesting and photoprotective functions of carotenoids in compact artificial photosynthetic antenna designs. / Kodis, Gerdenis; Herrero, Christian; Palacios, Rodrigo; Mariño-Ochoa, Ernesto; Gould, Stephanie; De La Garza, Linda; Van Grondelle, Rienk; Gust, John Devens; Moore, Thomas A; Moore, Ana L; Kennis, John T M.

In: Journal of Physical Chemistry B, Vol. 108, No. 1, 08.01.2004, p. 414-425.

Research output: Contribution to journalArticle

Kodis, G, Herrero, C, Palacios, R, Mariño-Ochoa, E, Gould, S, De La Garza, L, Van Grondelle, R, Gust, JD, Moore, TA, Moore, AL & Kennis, JTM 2004, 'Light harvesting and photoprotective functions of carotenoids in compact artificial photosynthetic antenna designs', Journal of Physical Chemistry B, vol. 108, no. 1, pp. 414-425.
Kodis G, Herrero C, Palacios R, Mariño-Ochoa E, Gould S, De La Garza L et al. Light harvesting and photoprotective functions of carotenoids in compact artificial photosynthetic antenna designs. Journal of Physical Chemistry B. 2004 Jan 8;108(1):414-425.
Kodis, Gerdenis ; Herrero, Christian ; Palacios, Rodrigo ; Mariño-Ochoa, Ernesto ; Gould, Stephanie ; De La Garza, Linda ; Van Grondelle, Rienk ; Gust, John Devens ; Moore, Thomas A ; Moore, Ana L ; Kennis, John T M. / Light harvesting and photoprotective functions of carotenoids in compact artificial photosynthetic antenna designs. In: Journal of Physical Chemistry B. 2004 ; Vol. 108, No. 1. pp. 414-425.
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