A molecular probe of the electric field produced by a photogenerated ion pair

Martin P. Debreczeny, Walter A. Svec, Michael R Wasielewski

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The electric field photogenerated by an electron donor-acceptor pair is probed with a covalently attached dye molecule using transient absorption spectroscopy. The donor molecule, 4-X-naphthalene-1,8-dicarboximide (Dx) (where X is (1) piperidine or (2) pyrrolidine), is directly attached to the 1,4,5,8-naphthalenetetracarboxydiimide acceptor (A), which is attached through a benzene spacer to the probe molecule, 4,4-difluoro-3,5-dimethyl-4-bora-3a, 4a-diaza-s-indacene (P). A ~150fs laser pulse at 412nm selectively excites Dx. The transition dipole of P is approximately perpendicular to the direction of the electric field generated by DX-A~, minimizing the rate of excitation energy transfer from DJ to P, whereas the maximum change in the state dipole upon excitation is parallel to the electric field, maximizing Stark-shift effects. The groundstate absorption spectrum of P in 1,4-dioxane (Ama)( = 512 nm) blue-shifts 5 + 1 nm and bleaches as the nearby radical pair (DX-A~) forms. The band-shift effect diminishes in the higher polarity solvents tetrahydrofuran and butyronitrile but does not disappear completely. Solvatochromism measurements performed at room temperature and conventional electrochromism measurements performed at 77 K on P alone, indicate that the state dipole of P decreases by 2.0+0.2 D upon excitation to the first excited singlet state. From this change in dipole moment and the observed band-shift in DX-A-P, the effective electric field due to the charge-separated pair, experienced by P in 1,4-dioxane, is found to be 6±1 MV/cm. '

Original languageEnglish
Pages (from-to)815-828
Number of pages14
JournalNew Journal of Chemistry
Volume20
Issue number7-8
Publication statusPublished - 1996

Fingerprint

Molecular Probes
Electric fields
Ions
Molecules
Electrochromism
Excitation energy
Dipole moment
Naphthalene
Benzene
Absorption spectroscopy
Excited states
Energy transfer
Absorption spectra
Laser pulses
Coloring Agents
Dyes
Electrons
Temperature
1,4-dioxane

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

A molecular probe of the electric field produced by a photogenerated ion pair. / Debreczeny, Martin P.; Svec, Walter A.; Wasielewski, Michael R.

In: New Journal of Chemistry, Vol. 20, No. 7-8, 1996, p. 815-828.

Research output: Contribution to journalArticle

Debreczeny, Martin P. ; Svec, Walter A. ; Wasielewski, Michael R. / A molecular probe of the electric field produced by a photogenerated ion pair. In: New Journal of Chemistry. 1996 ; Vol. 20, No. 7-8. pp. 815-828.
@article{9bc5ef8ac6384415bb1ad3108fd77e68,
title = "A molecular probe of the electric field produced by a photogenerated ion pair",
abstract = "The electric field photogenerated by an electron donor-acceptor pair is probed with a covalently attached dye molecule using transient absorption spectroscopy. The donor molecule, 4-X-naphthalene-1,8-dicarboximide (Dx) (where X is (1) piperidine or (2) pyrrolidine), is directly attached to the 1,4,5,8-naphthalenetetracarboxydiimide acceptor (A), which is attached through a benzene spacer to the probe molecule, 4,4-difluoro-3,5-dimethyl-4-bora-3a, 4a-diaza-s-indacene (P). A ~150fs laser pulse at 412nm selectively excites Dx. The transition dipole of P is approximately perpendicular to the direction of the electric field generated by DX-A~, minimizing the rate of excitation energy transfer from DJ to P, whereas the maximum change in the state dipole upon excitation is parallel to the electric field, maximizing Stark-shift effects. The groundstate absorption spectrum of P in 1,4-dioxane (Ama)( = 512 nm) blue-shifts 5 + 1 nm and bleaches as the nearby radical pair (DX-A~) forms. The band-shift effect diminishes in the higher polarity solvents tetrahydrofuran and butyronitrile but does not disappear completely. Solvatochromism measurements performed at room temperature and conventional electrochromism measurements performed at 77 K on P alone, indicate that the state dipole of P decreases by 2.0+0.2 D upon excitation to the first excited singlet state. From this change in dipole moment and the observed band-shift in DX-A-P, the effective electric field due to the charge-separated pair, experienced by P in 1,4-dioxane, is found to be 6±1 MV/cm. '",
author = "Debreczeny, {Martin P.} and Svec, {Walter A.} and Wasielewski, {Michael R}",
year = "1996",
language = "English",
volume = "20",
pages = "815--828",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "7-8",

}

TY - JOUR

T1 - A molecular probe of the electric field produced by a photogenerated ion pair

AU - Debreczeny, Martin P.

AU - Svec, Walter A.

AU - Wasielewski, Michael R

PY - 1996

Y1 - 1996

N2 - The electric field photogenerated by an electron donor-acceptor pair is probed with a covalently attached dye molecule using transient absorption spectroscopy. The donor molecule, 4-X-naphthalene-1,8-dicarboximide (Dx) (where X is (1) piperidine or (2) pyrrolidine), is directly attached to the 1,4,5,8-naphthalenetetracarboxydiimide acceptor (A), which is attached through a benzene spacer to the probe molecule, 4,4-difluoro-3,5-dimethyl-4-bora-3a, 4a-diaza-s-indacene (P). A ~150fs laser pulse at 412nm selectively excites Dx. The transition dipole of P is approximately perpendicular to the direction of the electric field generated by DX-A~, minimizing the rate of excitation energy transfer from DJ to P, whereas the maximum change in the state dipole upon excitation is parallel to the electric field, maximizing Stark-shift effects. The groundstate absorption spectrum of P in 1,4-dioxane (Ama)( = 512 nm) blue-shifts 5 + 1 nm and bleaches as the nearby radical pair (DX-A~) forms. The band-shift effect diminishes in the higher polarity solvents tetrahydrofuran and butyronitrile but does not disappear completely. Solvatochromism measurements performed at room temperature and conventional electrochromism measurements performed at 77 K on P alone, indicate that the state dipole of P decreases by 2.0+0.2 D upon excitation to the first excited singlet state. From this change in dipole moment and the observed band-shift in DX-A-P, the effective electric field due to the charge-separated pair, experienced by P in 1,4-dioxane, is found to be 6±1 MV/cm. '

AB - The electric field photogenerated by an electron donor-acceptor pair is probed with a covalently attached dye molecule using transient absorption spectroscopy. The donor molecule, 4-X-naphthalene-1,8-dicarboximide (Dx) (where X is (1) piperidine or (2) pyrrolidine), is directly attached to the 1,4,5,8-naphthalenetetracarboxydiimide acceptor (A), which is attached through a benzene spacer to the probe molecule, 4,4-difluoro-3,5-dimethyl-4-bora-3a, 4a-diaza-s-indacene (P). A ~150fs laser pulse at 412nm selectively excites Dx. The transition dipole of P is approximately perpendicular to the direction of the electric field generated by DX-A~, minimizing the rate of excitation energy transfer from DJ to P, whereas the maximum change in the state dipole upon excitation is parallel to the electric field, maximizing Stark-shift effects. The groundstate absorption spectrum of P in 1,4-dioxane (Ama)( = 512 nm) blue-shifts 5 + 1 nm and bleaches as the nearby radical pair (DX-A~) forms. The band-shift effect diminishes in the higher polarity solvents tetrahydrofuran and butyronitrile but does not disappear completely. Solvatochromism measurements performed at room temperature and conventional electrochromism measurements performed at 77 K on P alone, indicate that the state dipole of P decreases by 2.0+0.2 D upon excitation to the first excited singlet state. From this change in dipole moment and the observed band-shift in DX-A-P, the effective electric field due to the charge-separated pair, experienced by P in 1,4-dioxane, is found to be 6±1 MV/cm. '

UR - http://www.scopus.com/inward/record.url?scp=0000387387&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000387387&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000387387

VL - 20

SP - 815

EP - 828

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 7-8

ER -