Spin-selective charge transport pathways through p-oligophenylene-linked donor-bridge-acceptor molecules

Amy M. Scott, Tomoaki Miura, Annie Butler Ricks, Zachary E X Dance, Emilie M. Giacobbe, Michael T. Colvin, Michael R Wasielewski

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

A series of donor-bridge-acceptor (D-B-A) triads have been synthesized in which the donor, 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An), and the acceptor, naphthalene-1,8:4,5-bis(dicarboximide) (NI), are linked by p-oligophenylene (Phn) bridging units (n = 1-5). Photoexcitation of DMJ-An produces DMJ+•-An-• quantitatively, so that An--• acts as a high potential electron donor, which rapidly transfers an electron to NI yielding a long-lived spin-coherent radical ion pair (DMJ+•-An-Phn-NI-•). The charge transfer properties of 1-5 have been studied using transient absorption spectroscopy, magnetic field effects (MFEs) on radical pair and triplet yields, and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The charge separation (CS) and recombination (CR) reactions exhibit exponential distance dependencies with damping coefficients of β = 0.35 Å-1 and 0.34 Å-1, respectively. Based on these data, a change in mechanism from superexchange to hopping was not observed for either process in this system. However, the CR reaction is spin-selective and produces the singlet ground state and both 3*An and 3*NI. A kinetic analysis of the MFE data shows that superexchange dominates both pathways with β = 0.48 Å-1 for the singlet CR pathway and β = 0.35 Å-1 for the triplet CR pathway. MFEs and TREPR experiments were used to measure the spin-spin exchange interaction, 2J, which is directly related to the electronic coupling matrix element for CR, VCR 2. The magnitude of 2J also shows an exponential distance dependence with a damping coefficient α = 0.36 Å-1, which agrees with the β values obtained from the distance dependence for triplet CR. These results were analyzed in terms of the bridge molecular orbitals that participate in the charge transport mechanism.

Original languageEnglish
Pages (from-to)17655-17666
Number of pages12
JournalJournal of the American Chemical Society
Volume131
Issue number48
DOIs
Publication statusPublished - Dec 9 2009

Fingerprint

Magnetic field effects
Genetic Recombination
Charge transfer
Molecules
Paramagnetic resonance
Magnetic Fields
Damping
Electrons
Photoexcitation
Exchange interactions
Electron Spin Resonance Spectroscopy
Molecular orbitals
Naphthalene
Absorption spectroscopy
Ground state
Spectrum Analysis
Spectroscopy
Kinetics
Ions
3,5-dimethyl-4-(9-anthracenyl)julolidine

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Spin-selective charge transport pathways through p-oligophenylene-linked donor-bridge-acceptor molecules. / Scott, Amy M.; Miura, Tomoaki; Ricks, Annie Butler; Dance, Zachary E X; Giacobbe, Emilie M.; Colvin, Michael T.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 131, No. 48, 09.12.2009, p. 17655-17666.

Research output: Contribution to journalArticle

Scott, Amy M. ; Miura, Tomoaki ; Ricks, Annie Butler ; Dance, Zachary E X ; Giacobbe, Emilie M. ; Colvin, Michael T. ; Wasielewski, Michael R. / Spin-selective charge transport pathways through p-oligophenylene-linked donor-bridge-acceptor molecules. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 48. pp. 17655-17666.
@article{6ae77211773743ef84153c1e8484e104,
title = "Spin-selective charge transport pathways through p-oligophenylene-linked donor-bridge-acceptor molecules",
abstract = "A series of donor-bridge-acceptor (D-B-A) triads have been synthesized in which the donor, 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An), and the acceptor, naphthalene-1,8:4,5-bis(dicarboximide) (NI), are linked by p-oligophenylene (Phn) bridging units (n = 1-5). Photoexcitation of DMJ-An produces DMJ+•-An-• quantitatively, so that An--• acts as a high potential electron donor, which rapidly transfers an electron to NI yielding a long-lived spin-coherent radical ion pair (DMJ+•-An-Phn-NI-•). The charge transfer properties of 1-5 have been studied using transient absorption spectroscopy, magnetic field effects (MFEs) on radical pair and triplet yields, and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The charge separation (CS) and recombination (CR) reactions exhibit exponential distance dependencies with damping coefficients of β = 0.35 {\AA}-1 and 0.34 {\AA}-1, respectively. Based on these data, a change in mechanism from superexchange to hopping was not observed for either process in this system. However, the CR reaction is spin-selective and produces the singlet ground state and both 3*An and 3*NI. A kinetic analysis of the MFE data shows that superexchange dominates both pathways with β = 0.48 {\AA}-1 for the singlet CR pathway and β = 0.35 {\AA}-1 for the triplet CR pathway. MFEs and TREPR experiments were used to measure the spin-spin exchange interaction, 2J, which is directly related to the electronic coupling matrix element for CR, VCR 2. The magnitude of 2J also shows an exponential distance dependence with a damping coefficient α = 0.36 {\AA}-1, which agrees with the β values obtained from the distance dependence for triplet CR. These results were analyzed in terms of the bridge molecular orbitals that participate in the charge transport mechanism.",
author = "Scott, {Amy M.} and Tomoaki Miura and Ricks, {Annie Butler} and Dance, {Zachary E X} and Giacobbe, {Emilie M.} and Colvin, {Michael T.} and Wasielewski, {Michael R}",
year = "2009",
month = "12",
day = "9",
doi = "10.1021/ja907625k",
language = "English",
volume = "131",
pages = "17655--17666",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "48",

}

TY - JOUR

T1 - Spin-selective charge transport pathways through p-oligophenylene-linked donor-bridge-acceptor molecules

AU - Scott, Amy M.

AU - Miura, Tomoaki

AU - Ricks, Annie Butler

AU - Dance, Zachary E X

AU - Giacobbe, Emilie M.

AU - Colvin, Michael T.

AU - Wasielewski, Michael R

PY - 2009/12/9

Y1 - 2009/12/9

N2 - A series of donor-bridge-acceptor (D-B-A) triads have been synthesized in which the donor, 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An), and the acceptor, naphthalene-1,8:4,5-bis(dicarboximide) (NI), are linked by p-oligophenylene (Phn) bridging units (n = 1-5). Photoexcitation of DMJ-An produces DMJ+•-An-• quantitatively, so that An--• acts as a high potential electron donor, which rapidly transfers an electron to NI yielding a long-lived spin-coherent radical ion pair (DMJ+•-An-Phn-NI-•). The charge transfer properties of 1-5 have been studied using transient absorption spectroscopy, magnetic field effects (MFEs) on radical pair and triplet yields, and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The charge separation (CS) and recombination (CR) reactions exhibit exponential distance dependencies with damping coefficients of β = 0.35 Å-1 and 0.34 Å-1, respectively. Based on these data, a change in mechanism from superexchange to hopping was not observed for either process in this system. However, the CR reaction is spin-selective and produces the singlet ground state and both 3*An and 3*NI. A kinetic analysis of the MFE data shows that superexchange dominates both pathways with β = 0.48 Å-1 for the singlet CR pathway and β = 0.35 Å-1 for the triplet CR pathway. MFEs and TREPR experiments were used to measure the spin-spin exchange interaction, 2J, which is directly related to the electronic coupling matrix element for CR, VCR 2. The magnitude of 2J also shows an exponential distance dependence with a damping coefficient α = 0.36 Å-1, which agrees with the β values obtained from the distance dependence for triplet CR. These results were analyzed in terms of the bridge molecular orbitals that participate in the charge transport mechanism.

AB - A series of donor-bridge-acceptor (D-B-A) triads have been synthesized in which the donor, 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An), and the acceptor, naphthalene-1,8:4,5-bis(dicarboximide) (NI), are linked by p-oligophenylene (Phn) bridging units (n = 1-5). Photoexcitation of DMJ-An produces DMJ+•-An-• quantitatively, so that An--• acts as a high potential electron donor, which rapidly transfers an electron to NI yielding a long-lived spin-coherent radical ion pair (DMJ+•-An-Phn-NI-•). The charge transfer properties of 1-5 have been studied using transient absorption spectroscopy, magnetic field effects (MFEs) on radical pair and triplet yields, and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The charge separation (CS) and recombination (CR) reactions exhibit exponential distance dependencies with damping coefficients of β = 0.35 Å-1 and 0.34 Å-1, respectively. Based on these data, a change in mechanism from superexchange to hopping was not observed for either process in this system. However, the CR reaction is spin-selective and produces the singlet ground state and both 3*An and 3*NI. A kinetic analysis of the MFE data shows that superexchange dominates both pathways with β = 0.48 Å-1 for the singlet CR pathway and β = 0.35 Å-1 for the triplet CR pathway. MFEs and TREPR experiments were used to measure the spin-spin exchange interaction, 2J, which is directly related to the electronic coupling matrix element for CR, VCR 2. The magnitude of 2J also shows an exponential distance dependence with a damping coefficient α = 0.36 Å-1, which agrees with the β values obtained from the distance dependence for triplet CR. These results were analyzed in terms of the bridge molecular orbitals that participate in the charge transport mechanism.

UR - http://www.scopus.com/inward/record.url?scp=72249111972&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=72249111972&partnerID=8YFLogxK

U2 - 10.1021/ja907625k

DO - 10.1021/ja907625k

M3 - Article

VL - 131

SP - 17655

EP - 17666

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 48

ER -