Factoring through-space and through-bond contributions to rates of photoinduced electron transfer in donor-spacer-acceptor molecules

David Gosztola, Bing Wang, Michael R Wasielewski

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Abstract

Contributions from direct orbital overlap (through-space interactions) and superexchange (through-bond interactions) to the electronic coupling matrix elements for photoinduced charge separation and recombination in a series of linked donor-spacer-acceptor molecules were studied. The molecules consisted of a 4-piperidinyl-naphthalene-1,8-dicarboximide (ANI) electron donor and a N-(n-octyl)pyromellitimide (PI) electron acceptor attached to the 1,5- and 1,8-positions of either anthracene (ANC) or dibenzobicyclo(2.2.2)octatriene (DBO) spacers. For the 1,8-disubstituted compounds, ANI and PI are held approximately cofacial with a center-to-center distance of 5.3 Å, whereas for the 1,5-disubstituted compounds, the center-to-center distance increases to 13.5 Å. The through-bond interaction was investigated by replacing the ANC spacer with DBO. The charge separation and recombination reactions were examined in both toluene and tetrahydrofuran (THF). The results show that for the 1,8-disubstituted DBO system in both toluene and THF, charge separation and recombination is dominated by through-space interactions. For the 1,8-disubstituted ANC system in both toluene and THF, charge separation occurs by means of a direct, through-space interaction, while charge recombination occurs through the intermediacy of the ANI - ANC+ - PI- ion pair in toluene and directly from ANI+ - ANC - PI- to ground state in THF. For the 1,5-disubstituted molecules, possessing either the ANC or the DBO spacers, electron transfer from 1*ANI to PI was not kinetically competitive with the decay of 1*ANI to ground state in either toluene or THF.

Original languageEnglish
Pages (from-to)71-80
Number of pages10
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume102
Issue number1
DOIs
Publication statusPublished - Dec 27 1996

Fingerprint

Anthracene
anthracene
spacers
Toluene
tetrahydrofuran
electron transfer
toluene
polarization (charge separation)
Molecules
Electrons
molecules
Ground state
interactions
recombination reactions
ground state
Naphthalene
naphthalene
electrons
Ions
orbitals

Keywords

  • Donor-spacer-acceptor molecules
  • Photoinduced electron transfer
  • Through-bond interactions
  • Through-space interactions

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

@article{22e31f2429234da8bb689f9f901fecda,
title = "Factoring through-space and through-bond contributions to rates of photoinduced electron transfer in donor-spacer-acceptor molecules",
abstract = "Contributions from direct orbital overlap (through-space interactions) and superexchange (through-bond interactions) to the electronic coupling matrix elements for photoinduced charge separation and recombination in a series of linked donor-spacer-acceptor molecules were studied. The molecules consisted of a 4-piperidinyl-naphthalene-1,8-dicarboximide (ANI) electron donor and a N-(n-octyl)pyromellitimide (PI) electron acceptor attached to the 1,5- and 1,8-positions of either anthracene (ANC) or dibenzobicyclo(2.2.2)octatriene (DBO) spacers. For the 1,8-disubstituted compounds, ANI and PI are held approximately cofacial with a center-to-center distance of 5.3 {\AA}, whereas for the 1,5-disubstituted compounds, the center-to-center distance increases to 13.5 {\AA}. The through-bond interaction was investigated by replacing the ANC spacer with DBO. The charge separation and recombination reactions were examined in both toluene and tetrahydrofuran (THF). The results show that for the 1,8-disubstituted DBO system in both toluene and THF, charge separation and recombination is dominated by through-space interactions. For the 1,8-disubstituted ANC system in both toluene and THF, charge separation occurs by means of a direct, through-space interaction, while charge recombination occurs through the intermediacy of the ANI - ANC+ - PI- ion pair in toluene and directly from ANI+ - ANC - PI- to ground state in THF. For the 1,5-disubstituted molecules, possessing either the ANC or the DBO spacers, electron transfer from 1*ANI to PI was not kinetically competitive with the decay of 1*ANI to ground state in either toluene or THF.",
keywords = "Donor-spacer-acceptor molecules, Photoinduced electron transfer, Through-bond interactions, Through-space interactions",
author = "David Gosztola and Bing Wang and Wasielewski, {Michael R}",
year = "1996",
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T1 - Factoring through-space and through-bond contributions to rates of photoinduced electron transfer in donor-spacer-acceptor molecules

AU - Gosztola, David

AU - Wang, Bing

AU - Wasielewski, Michael R

PY - 1996/12/27

Y1 - 1996/12/27

N2 - Contributions from direct orbital overlap (through-space interactions) and superexchange (through-bond interactions) to the electronic coupling matrix elements for photoinduced charge separation and recombination in a series of linked donor-spacer-acceptor molecules were studied. The molecules consisted of a 4-piperidinyl-naphthalene-1,8-dicarboximide (ANI) electron donor and a N-(n-octyl)pyromellitimide (PI) electron acceptor attached to the 1,5- and 1,8-positions of either anthracene (ANC) or dibenzobicyclo(2.2.2)octatriene (DBO) spacers. For the 1,8-disubstituted compounds, ANI and PI are held approximately cofacial with a center-to-center distance of 5.3 Å, whereas for the 1,5-disubstituted compounds, the center-to-center distance increases to 13.5 Å. The through-bond interaction was investigated by replacing the ANC spacer with DBO. The charge separation and recombination reactions were examined in both toluene and tetrahydrofuran (THF). The results show that for the 1,8-disubstituted DBO system in both toluene and THF, charge separation and recombination is dominated by through-space interactions. For the 1,8-disubstituted ANC system in both toluene and THF, charge separation occurs by means of a direct, through-space interaction, while charge recombination occurs through the intermediacy of the ANI - ANC+ - PI- ion pair in toluene and directly from ANI+ - ANC - PI- to ground state in THF. For the 1,5-disubstituted molecules, possessing either the ANC or the DBO spacers, electron transfer from 1*ANI to PI was not kinetically competitive with the decay of 1*ANI to ground state in either toluene or THF.

AB - Contributions from direct orbital overlap (through-space interactions) and superexchange (through-bond interactions) to the electronic coupling matrix elements for photoinduced charge separation and recombination in a series of linked donor-spacer-acceptor molecules were studied. The molecules consisted of a 4-piperidinyl-naphthalene-1,8-dicarboximide (ANI) electron donor and a N-(n-octyl)pyromellitimide (PI) electron acceptor attached to the 1,5- and 1,8-positions of either anthracene (ANC) or dibenzobicyclo(2.2.2)octatriene (DBO) spacers. For the 1,8-disubstituted compounds, ANI and PI are held approximately cofacial with a center-to-center distance of 5.3 Å, whereas for the 1,5-disubstituted compounds, the center-to-center distance increases to 13.5 Å. The through-bond interaction was investigated by replacing the ANC spacer with DBO. The charge separation and recombination reactions were examined in both toluene and tetrahydrofuran (THF). The results show that for the 1,8-disubstituted DBO system in both toluene and THF, charge separation and recombination is dominated by through-space interactions. For the 1,8-disubstituted ANC system in both toluene and THF, charge separation occurs by means of a direct, through-space interaction, while charge recombination occurs through the intermediacy of the ANI - ANC+ - PI- ion pair in toluene and directly from ANI+ - ANC - PI- to ground state in THF. For the 1,5-disubstituted molecules, possessing either the ANC or the DBO spacers, electron transfer from 1*ANI to PI was not kinetically competitive with the decay of 1*ANI to ground state in either toluene or THF.

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KW - Through-space interactions

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