Polarity-tuned energy transfer efficiency in artificial light-harvesting antennae containing carbonyl carotenoids peridinin and fucoxanthin
(2007) In Journal of Physical Chemistry C 111(1). p.467-476- Abstract
- This study focuses on the mechanisms and pathways of energy transfer in two carotenoid-pyropheophorbide dyads serving as an artificial light-harvesting antenna. The dyads contain carbonyl carotenoids peridinin (dyad 1) and fucoxanthin ( dyad 2). Studies of these carotenoids in solution showed a pronounced dependence of the excited-state lifetime on solvent polarity. This dependence was attributed to the presence of a state with intramolecular charge transfer (ICT) character in the excited-state manifold. Here we measured carotenoid-pyropheophorbide energy transfer in solvents with different polarity. Energy transfer occurs on a time scale of 31-44 ps for dyad 1, but it is nearly an order of magnitude slower for dyad 2 (195-280 ps). Energy... (More)
- This study focuses on the mechanisms and pathways of energy transfer in two carotenoid-pyropheophorbide dyads serving as an artificial light-harvesting antenna. The dyads contain carbonyl carotenoids peridinin (dyad 1) and fucoxanthin ( dyad 2). Studies of these carotenoids in solution showed a pronounced dependence of the excited-state lifetime on solvent polarity. This dependence was attributed to the presence of a state with intramolecular charge transfer (ICT) character in the excited-state manifold. Here we measured carotenoid-pyropheophorbide energy transfer in solvents with different polarity. Energy transfer occurs on a time scale of 31-44 ps for dyad 1, but it is nearly an order of magnitude slower for dyad 2 (195-280 ps). Energy transfer efficiency varies with solvent polarity, reaching 80% in benzene, 69% in tetrahydrofuran, and 22% in acetonitrile for dyad 1 and 27% in benzene, 19% in tetrahydrofuran, and 13% in acetonitrile for dyad 2. The factors controlling this polarity dependence are (1) the competition of energy transfer rate with the S-1/ICT lifetime, which, for carbonyl carotenoids, is significantly shorter in polar solvents, ( 2) the mutual orientation of the carotenoid and pyropheophorbide moieties, and (3) enhancement of the S-1/ICT dipole moment by increasing the ICT character of the S-1/ICT state in polar solvents. The possibility of tuning energy transfer through solvent polarity in combination with another spectroscopic feature of carbonyl carotenoids, efficient absorption of light in the spectral region close to the maximum of the solar irradiance curve (450-550 nm), makes these dyads attractive for potential application as artificial antenna. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/670073
- author
- Polivka, Tomas LU ; Pellnor, Mathias ; Melo, Eurico ; Pascher, Torbjörn LU ; Sundström, Villy LU ; Osuka, Atsuhiro and Naqvi, K. Razi
- organization
- publishing date
- 2007
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Physical Chemistry C
- volume
- 111
- issue
- 1
- pages
- 467 - 476
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000244993800069
- scopus:33847659747
- ISSN
- 1932-7447
- DOI
- 10.1021/jp066187j
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- b01ebf86-c6bf-4d1c-b692-8306ae4e35dd (old id 670073)
- date added to LUP
- 2016-04-01 11:49:27
- date last changed
- 2022-03-20 19:28:13
@article{b01ebf86-c6bf-4d1c-b692-8306ae4e35dd,
abstract = {{This study focuses on the mechanisms and pathways of energy transfer in two carotenoid-pyropheophorbide dyads serving as an artificial light-harvesting antenna. The dyads contain carbonyl carotenoids peridinin (dyad 1) and fucoxanthin ( dyad 2). Studies of these carotenoids in solution showed a pronounced dependence of the excited-state lifetime on solvent polarity. This dependence was attributed to the presence of a state with intramolecular charge transfer (ICT) character in the excited-state manifold. Here we measured carotenoid-pyropheophorbide energy transfer in solvents with different polarity. Energy transfer occurs on a time scale of 31-44 ps for dyad 1, but it is nearly an order of magnitude slower for dyad 2 (195-280 ps). Energy transfer efficiency varies with solvent polarity, reaching 80% in benzene, 69% in tetrahydrofuran, and 22% in acetonitrile for dyad 1 and 27% in benzene, 19% in tetrahydrofuran, and 13% in acetonitrile for dyad 2. The factors controlling this polarity dependence are (1) the competition of energy transfer rate with the S-1/ICT lifetime, which, for carbonyl carotenoids, is significantly shorter in polar solvents, ( 2) the mutual orientation of the carotenoid and pyropheophorbide moieties, and (3) enhancement of the S-1/ICT dipole moment by increasing the ICT character of the S-1/ICT state in polar solvents. The possibility of tuning energy transfer through solvent polarity in combination with another spectroscopic feature of carbonyl carotenoids, efficient absorption of light in the spectral region close to the maximum of the solar irradiance curve (450-550 nm), makes these dyads attractive for potential application as artificial antenna.}},
author = {{Polivka, Tomas and Pellnor, Mathias and Melo, Eurico and Pascher, Torbjörn and Sundström, Villy and Osuka, Atsuhiro and Naqvi, K. Razi}},
issn = {{1932-7447}},
language = {{eng}},
number = {{1}},
pages = {{467--476}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of Physical Chemistry C}},
title = {{Polarity-tuned energy transfer efficiency in artificial light-harvesting antennae containing carbonyl carotenoids peridinin and fucoxanthin}},
url = {{http://dx.doi.org/10.1021/jp066187j}},
doi = {{10.1021/jp066187j}},
volume = {{111}},
year = {{2007}},
}