Artificial photosynthetic reaction center with a coumarin-based antenna system

Vikas Garg, Gerdenis Kodis, Paul A. Liddell, Yuichi Terazono, Thomas A Moore, Ana L Moore, John Devens Gust

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

In photosynthesis, sunlight is absorbed mainly by antenna chromophores that transfer singlet excitation energy to reaction centers for conversion to useful electrochemical energy. Antennas may likewise be useful in artificial photosynthetic systems that use sunlight to make fuels or electricity. Here, we report the synthesis and spectroscopic properties of a molecular hexad comprising two porphyrin moieties and four coumarin antenna chromophores, all organized by a central hexaphenylbenzene core. Light absorbed by any of the coumarins is transferred to a porphyrin on the 1-10 ps time scale, depending on the site of initial excitation. The quantum yield of singlet energy transfer is 1.0. The energy transfer rate constants are consistent with transfer by the Förster dipole-dipole mechanism. A pyridyl-bearing fullerene moiety self-assembles to the form of the hexad containing zinc porphyrins to yield an antenna-reaction center complex. In the resulting heptad, energy transfer to the porphyrins is followed by photoinduced electron transfer to the fullerene with a time constant of 3 ps. The resulting P•+-C60 •- charge-separated state is formed with an overall quantum yield of 1.0 and decays with a time constant of 230 ps in 1,2-difluorobenzene as the solvent.

Original languageEnglish
Pages (from-to)11299-11308
Number of pages10
JournalJournal of Physical Chemistry B
Volume117
Issue number38
DOIs
Publication statusPublished - Sep 26 2013

Fingerprint

Photosynthetic Reaction Center Complex Proteins
Porphyrins
porphyrins
antennas
Energy transfer
Antennas
Fullerenes
energy transfer
Quantum yield
sunlight
Chromophores
chromophores
time constant
fullerenes
Bearings (structural)
dipoles
Coumarins
photosynthesis
Photosynthesis
Excitation energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Artificial photosynthetic reaction center with a coumarin-based antenna system. / Garg, Vikas; Kodis, Gerdenis; Liddell, Paul A.; Terazono, Yuichi; Moore, Thomas A; Moore, Ana L; Gust, John Devens.

In: Journal of Physical Chemistry B, Vol. 117, No. 38, 26.09.2013, p. 11299-11308.

Research output: Contribution to journalArticle

Garg, Vikas ; Kodis, Gerdenis ; Liddell, Paul A. ; Terazono, Yuichi ; Moore, Thomas A ; Moore, Ana L ; Gust, John Devens. / Artificial photosynthetic reaction center with a coumarin-based antenna system. In: Journal of Physical Chemistry B. 2013 ; Vol. 117, No. 38. pp. 11299-11308.
@article{168f48f2ef084540bd3c4de70be0225d,
title = "Artificial photosynthetic reaction center with a coumarin-based antenna system",
abstract = "In photosynthesis, sunlight is absorbed mainly by antenna chromophores that transfer singlet excitation energy to reaction centers for conversion to useful electrochemical energy. Antennas may likewise be useful in artificial photosynthetic systems that use sunlight to make fuels or electricity. Here, we report the synthesis and spectroscopic properties of a molecular hexad comprising two porphyrin moieties and four coumarin antenna chromophores, all organized by a central hexaphenylbenzene core. Light absorbed by any of the coumarins is transferred to a porphyrin on the 1-10 ps time scale, depending on the site of initial excitation. The quantum yield of singlet energy transfer is 1.0. The energy transfer rate constants are consistent with transfer by the F{\"o}rster dipole-dipole mechanism. A pyridyl-bearing fullerene moiety self-assembles to the form of the hexad containing zinc porphyrins to yield an antenna-reaction center complex. In the resulting heptad, energy transfer to the porphyrins is followed by photoinduced electron transfer to the fullerene with a time constant of 3 ps. The resulting P•+-C60 •- charge-separated state is formed with an overall quantum yield of 1.0 and decays with a time constant of 230 ps in 1,2-difluorobenzene as the solvent.",
author = "Vikas Garg and Gerdenis Kodis and Liddell, {Paul A.} and Yuichi Terazono and Moore, {Thomas A} and Moore, {Ana L} and Gust, {John Devens}",
year = "2013",
month = "9",
day = "26",
doi = "10.1021/jp402265e",
language = "English",
volume = "117",
pages = "11299--11308",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "38",

}

TY - JOUR

T1 - Artificial photosynthetic reaction center with a coumarin-based antenna system

AU - Garg, Vikas

AU - Kodis, Gerdenis

AU - Liddell, Paul A.

AU - Terazono, Yuichi

AU - Moore, Thomas A

AU - Moore, Ana L

AU - Gust, John Devens

PY - 2013/9/26

Y1 - 2013/9/26

N2 - In photosynthesis, sunlight is absorbed mainly by antenna chromophores that transfer singlet excitation energy to reaction centers for conversion to useful electrochemical energy. Antennas may likewise be useful in artificial photosynthetic systems that use sunlight to make fuels or electricity. Here, we report the synthesis and spectroscopic properties of a molecular hexad comprising two porphyrin moieties and four coumarin antenna chromophores, all organized by a central hexaphenylbenzene core. Light absorbed by any of the coumarins is transferred to a porphyrin on the 1-10 ps time scale, depending on the site of initial excitation. The quantum yield of singlet energy transfer is 1.0. The energy transfer rate constants are consistent with transfer by the Förster dipole-dipole mechanism. A pyridyl-bearing fullerene moiety self-assembles to the form of the hexad containing zinc porphyrins to yield an antenna-reaction center complex. In the resulting heptad, energy transfer to the porphyrins is followed by photoinduced electron transfer to the fullerene with a time constant of 3 ps. The resulting P•+-C60 •- charge-separated state is formed with an overall quantum yield of 1.0 and decays with a time constant of 230 ps in 1,2-difluorobenzene as the solvent.

AB - In photosynthesis, sunlight is absorbed mainly by antenna chromophores that transfer singlet excitation energy to reaction centers for conversion to useful electrochemical energy. Antennas may likewise be useful in artificial photosynthetic systems that use sunlight to make fuels or electricity. Here, we report the synthesis and spectroscopic properties of a molecular hexad comprising two porphyrin moieties and four coumarin antenna chromophores, all organized by a central hexaphenylbenzene core. Light absorbed by any of the coumarins is transferred to a porphyrin on the 1-10 ps time scale, depending on the site of initial excitation. The quantum yield of singlet energy transfer is 1.0. The energy transfer rate constants are consistent with transfer by the Förster dipole-dipole mechanism. A pyridyl-bearing fullerene moiety self-assembles to the form of the hexad containing zinc porphyrins to yield an antenna-reaction center complex. In the resulting heptad, energy transfer to the porphyrins is followed by photoinduced electron transfer to the fullerene with a time constant of 3 ps. The resulting P•+-C60 •- charge-separated state is formed with an overall quantum yield of 1.0 and decays with a time constant of 230 ps in 1,2-difluorobenzene as the solvent.

UR - http://www.scopus.com/inward/record.url?scp=84884972338&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84884972338&partnerID=8YFLogxK

U2 - 10.1021/jp402265e

DO - 10.1021/jp402265e

M3 - Article

C2 - 23534929

AN - SCOPUS:84884972338

VL - 117

SP - 11299

EP - 11308

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 38

ER -