Manipulation of the distance of light-induced electron transfer within a semi-rigid donor(amine)/acceptor(terpyridine) assembly via complexation of di-positive and tri-positive metal ions

Keith A. Walters, Young Jin Kim, Joseph T Hupp

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Electric field-effect spectroscopy techniques (electronic absorption and emission) have been applied to the problem of light-induced electron transfer (ET) within a covalently linked organic donor/acceptor pair. The spectroscopy measurements report on the change in the assembly's dipole moment upon ET. This quantity (the dipole-moment change) represents a direct measure of the distance over which the electron is transferred. The experiments show that the true charge transfer distance is much less than the geometric separation distance between the nominal electron donor and acceptor centers. The experiments additionally show that the transfer distance can be changed: binding of both open-shell and closed-shell metal cations with the acceptor portion of the assembly causes the ET distance to increase, with a tri-positive ion inducing a greater increase than di-positive ions. Electronic structure calculations qualitatively reproduce the experimental observations. From the calculations, the lengthening of the transfer distance is an electrostatic effect that appears to be associated primarily with a change in the shape of the orbital occupied by the transferred electron in the redox product state.

Original languageEnglish
Pages (from-to)449-458
Number of pages10
JournalJournal of Electroanalytical Chemistry
Volume554-555
Issue number1
DOIs
Publication statusPublished - Sep 15 2003

Fingerprint

Complexation
Amines
Metal ions
Positive ions
Electrons
Dipole moment
Spectroscopy
Electric field effects
Electronic structure
Cations
Charge transfer
Electrostatics
Metals
Experiments

Keywords

  • Charge transfer distance
  • Electric field-effect spectroscopy
  • Light-induced electron transfer

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

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title = "Manipulation of the distance of light-induced electron transfer within a semi-rigid donor(amine)/acceptor(terpyridine) assembly via complexation of di-positive and tri-positive metal ions",
abstract = "Electric field-effect spectroscopy techniques (electronic absorption and emission) have been applied to the problem of light-induced electron transfer (ET) within a covalently linked organic donor/acceptor pair. The spectroscopy measurements report on the change in the assembly's dipole moment upon ET. This quantity (the dipole-moment change) represents a direct measure of the distance over which the electron is transferred. The experiments show that the true charge transfer distance is much less than the geometric separation distance between the nominal electron donor and acceptor centers. The experiments additionally show that the transfer distance can be changed: binding of both open-shell and closed-shell metal cations with the acceptor portion of the assembly causes the ET distance to increase, with a tri-positive ion inducing a greater increase than di-positive ions. Electronic structure calculations qualitatively reproduce the experimental observations. From the calculations, the lengthening of the transfer distance is an electrostatic effect that appears to be associated primarily with a change in the shape of the orbital occupied by the transferred electron in the redox product state.",
keywords = "Charge transfer distance, Electric field-effect spectroscopy, Light-induced electron transfer",
author = "Walters, {Keith A.} and Kim, {Young Jin} and Hupp, {Joseph T}",
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T1 - Manipulation of the distance of light-induced electron transfer within a semi-rigid donor(amine)/acceptor(terpyridine) assembly via complexation of di-positive and tri-positive metal ions

AU - Walters, Keith A.

AU - Kim, Young Jin

AU - Hupp, Joseph T

PY - 2003/9/15

Y1 - 2003/9/15

N2 - Electric field-effect spectroscopy techniques (electronic absorption and emission) have been applied to the problem of light-induced electron transfer (ET) within a covalently linked organic donor/acceptor pair. The spectroscopy measurements report on the change in the assembly's dipole moment upon ET. This quantity (the dipole-moment change) represents a direct measure of the distance over which the electron is transferred. The experiments show that the true charge transfer distance is much less than the geometric separation distance between the nominal electron donor and acceptor centers. The experiments additionally show that the transfer distance can be changed: binding of both open-shell and closed-shell metal cations with the acceptor portion of the assembly causes the ET distance to increase, with a tri-positive ion inducing a greater increase than di-positive ions. Electronic structure calculations qualitatively reproduce the experimental observations. From the calculations, the lengthening of the transfer distance is an electrostatic effect that appears to be associated primarily with a change in the shape of the orbital occupied by the transferred electron in the redox product state.

AB - Electric field-effect spectroscopy techniques (electronic absorption and emission) have been applied to the problem of light-induced electron transfer (ET) within a covalently linked organic donor/acceptor pair. The spectroscopy measurements report on the change in the assembly's dipole moment upon ET. This quantity (the dipole-moment change) represents a direct measure of the distance over which the electron is transferred. The experiments show that the true charge transfer distance is much less than the geometric separation distance between the nominal electron donor and acceptor centers. The experiments additionally show that the transfer distance can be changed: binding of both open-shell and closed-shell metal cations with the acceptor portion of the assembly causes the ET distance to increase, with a tri-positive ion inducing a greater increase than di-positive ions. Electronic structure calculations qualitatively reproduce the experimental observations. From the calculations, the lengthening of the transfer distance is an electrostatic effect that appears to be associated primarily with a change in the shape of the orbital occupied by the transferred electron in the redox product state.

KW - Charge transfer distance

KW - Electric field-effect spectroscopy

KW - Light-induced electron transfer

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