Photoinduced electron transfer in a symmetrical diporphyrin-fullerene triad

Paul A. Liddell, Gerdenis Kodis, Darius Kuciauskas, Joakim Andréasson, Ana L Moore, Thomas A Moore, John Devens Gust

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Two triad molecules consisting of either two zinc, or two free-base porphyrins symmetrically joined to a fullerene via phenyleneethynylene- containing linkages have been synthesized, and their photochemistry investigated. In the zinc form of the triad. PZn-C 60-PZn, excitation of a zinc porphyrin in 2-methyltetrahydrofuran solution is followed by photoinduced electron transfer to the fullerene with a time constant of 20 ps. The resulting P Zn.+-C60.--PZn charge-separated state is formed with a quantum yield of 98% and has a lifetime of 820 ps. The first excited singlet state of the free-base analog gives the P2H.+-C60.--P2H charge-separated state with a time constant of 200 ps and a yield of 98%. The charge-separated state decays with a lifetime of 2.8 ns. The difference in the rates of photoinduced electron transfer is consistent with reaction in the normal region of the Marcus-Hush relationship of transfer rate and driving force, and charge recombination is consistent with Marcus-Hush inverted behavior. The presence of the two porphyrin electron donors in these triads enhances the absorption cross section for light collection, and the molecular framework employed could be used to prepare molecules with enhanced energy conversion or optoelectronic properties.

Original languageEnglish
Pages (from-to)5509-5515
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume6
Issue number24
DOIs
Publication statusPublished - Dec 21 2004

Fingerprint

Fullerenes
porphyrins
fullerenes
electron transfer
zinc
Porphyrins
time constant
Electrons
Zinc
life (durability)
Molecules
Photochemical reactions
energy conversion
Quantum yield
Energy conversion
Excited states
linkages
Optoelectronic devices
photochemical reactions
absorption cross sections

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Photoinduced electron transfer in a symmetrical diporphyrin-fullerene triad. / Liddell, Paul A.; Kodis, Gerdenis; Kuciauskas, Darius; Andréasson, Joakim; Moore, Ana L; Moore, Thomas A; Gust, John Devens.

In: Physical Chemistry Chemical Physics, Vol. 6, No. 24, 21.12.2004, p. 5509-5515.

Research output: Contribution to journalArticle

Liddell, Paul A. ; Kodis, Gerdenis ; Kuciauskas, Darius ; Andréasson, Joakim ; Moore, Ana L ; Moore, Thomas A ; Gust, John Devens. / Photoinduced electron transfer in a symmetrical diporphyrin-fullerene triad. In: Physical Chemistry Chemical Physics. 2004 ; Vol. 6, No. 24. pp. 5509-5515.
@article{fed4f4580fe64c468f8df1ee1b3b8955,
title = "Photoinduced electron transfer in a symmetrical diporphyrin-fullerene triad",
abstract = "Two triad molecules consisting of either two zinc, or two free-base porphyrins symmetrically joined to a fullerene via phenyleneethynylene- containing linkages have been synthesized, and their photochemistry investigated. In the zinc form of the triad. PZn-C 60-PZn, excitation of a zinc porphyrin in 2-methyltetrahydrofuran solution is followed by photoinduced electron transfer to the fullerene with a time constant of 20 ps. The resulting P Zn.+-C60.--PZn charge-separated state is formed with a quantum yield of 98{\%} and has a lifetime of 820 ps. The first excited singlet state of the free-base analog gives the P2H.+-C60.--P2H charge-separated state with a time constant of 200 ps and a yield of 98{\%}. The charge-separated state decays with a lifetime of 2.8 ns. The difference in the rates of photoinduced electron transfer is consistent with reaction in the normal region of the Marcus-Hush relationship of transfer rate and driving force, and charge recombination is consistent with Marcus-Hush inverted behavior. The presence of the two porphyrin electron donors in these triads enhances the absorption cross section for light collection, and the molecular framework employed could be used to prepare molecules with enhanced energy conversion or optoelectronic properties.",
author = "Liddell, {Paul A.} and Gerdenis Kodis and Darius Kuciauskas and Joakim Andr{\'e}asson and Moore, {Ana L} and Moore, {Thomas A} and Gust, {John Devens}",
year = "2004",
month = "12",
day = "21",
doi = "10.1039/b412326c",
language = "English",
volume = "6",
pages = "5509--5515",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "24",

}

TY - JOUR

T1 - Photoinduced electron transfer in a symmetrical diporphyrin-fullerene triad

AU - Liddell, Paul A.

AU - Kodis, Gerdenis

AU - Kuciauskas, Darius

AU - Andréasson, Joakim

AU - Moore, Ana L

AU - Moore, Thomas A

AU - Gust, John Devens

PY - 2004/12/21

Y1 - 2004/12/21

N2 - Two triad molecules consisting of either two zinc, or two free-base porphyrins symmetrically joined to a fullerene via phenyleneethynylene- containing linkages have been synthesized, and their photochemistry investigated. In the zinc form of the triad. PZn-C 60-PZn, excitation of a zinc porphyrin in 2-methyltetrahydrofuran solution is followed by photoinduced electron transfer to the fullerene with a time constant of 20 ps. The resulting P Zn.+-C60.--PZn charge-separated state is formed with a quantum yield of 98% and has a lifetime of 820 ps. The first excited singlet state of the free-base analog gives the P2H.+-C60.--P2H charge-separated state with a time constant of 200 ps and a yield of 98%. The charge-separated state decays with a lifetime of 2.8 ns. The difference in the rates of photoinduced electron transfer is consistent with reaction in the normal region of the Marcus-Hush relationship of transfer rate and driving force, and charge recombination is consistent with Marcus-Hush inverted behavior. The presence of the two porphyrin electron donors in these triads enhances the absorption cross section for light collection, and the molecular framework employed could be used to prepare molecules with enhanced energy conversion or optoelectronic properties.

AB - Two triad molecules consisting of either two zinc, or two free-base porphyrins symmetrically joined to a fullerene via phenyleneethynylene- containing linkages have been synthesized, and their photochemistry investigated. In the zinc form of the triad. PZn-C 60-PZn, excitation of a zinc porphyrin in 2-methyltetrahydrofuran solution is followed by photoinduced electron transfer to the fullerene with a time constant of 20 ps. The resulting P Zn.+-C60.--PZn charge-separated state is formed with a quantum yield of 98% and has a lifetime of 820 ps. The first excited singlet state of the free-base analog gives the P2H.+-C60.--P2H charge-separated state with a time constant of 200 ps and a yield of 98%. The charge-separated state decays with a lifetime of 2.8 ns. The difference in the rates of photoinduced electron transfer is consistent with reaction in the normal region of the Marcus-Hush relationship of transfer rate and driving force, and charge recombination is consistent with Marcus-Hush inverted behavior. The presence of the two porphyrin electron donors in these triads enhances the absorption cross section for light collection, and the molecular framework employed could be used to prepare molecules with enhanced energy conversion or optoelectronic properties.

UR - http://www.scopus.com/inward/record.url?scp=11244253804&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=11244253804&partnerID=8YFLogxK

U2 - 10.1039/b412326c

DO - 10.1039/b412326c

M3 - Article

VL - 6

SP - 5509

EP - 5515

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 24

ER -