Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4

9,10-bis(dicarboximide) Donor-Acceptor Dyads

Guan Jhih Huang, Michelle A. Harris, Matthew D. Krzyaniak, Eric A. Margulies, Scott M. Dyar, Rebecca J. Lindquist, Yilei Wu, Vladimir V. Roznyatovskiy, Yi Lin Wu, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Connecting electron donors and acceptors to a benzene ring in a meta or para relationship results in quantum interference effects that can strongly influence charge separation (CS) and charge recombination (CR) processes in these systems. We report on the energy and electron transfer behavior of chlorophyll-based para- and meta-linked donor-bridge-acceptor (D-B-A) dyads, where the semisynthetic chlorophyll a derivative, zinc methyl 3-ethyl-pyrochlorophyllide a (D), is covalently attached at its 20-position to the para position of one phenyl of diphenylacetylene (B). The meta or para position of the phenyl in B distal to the donor is in turn attached to perylene-3,4:9,10-bis(dicarboximide) (PDI) (A). Photoexcitation of the D-B-A dyads produces long-lived radical ion pairs D•+-B-A•-, which recombine to the ground state and to both 3∗D-B-A and D-B-3∗A. Time-resolved optical and electron paramagnetic resonance spectroscopies were used to monitor the charge transfer and triplet energy transfer (TEnT) processes. At longer times, TEnT occurs from 3∗D-B-A to D-B-3∗A. Surprisingly, the D-B-A molecules linked via the meta linkage exhibit faster CS, CR, and TEnT rates than do those with the para linkage in contrast to most other meta/para-linked D-B-A molecules previously examined.

Original languageEnglish
Pages (from-to)756-765
Number of pages10
JournalJournal of Physical Chemistry B
Volume120
Issue number4
DOIs
Publication statusPublished - Feb 4 2016

Fingerprint

Perylene
chlorophylls
Chlorophyll
Energy transfer
Charge transfer
energy transfer
charge transfer
polarization (charge separation)
linkages
Molecules
Electrons
Photoexcitation
Benzene
photoexcitation
Ground state
Paramagnetic resonance
Zinc
molecules
electron paramagnetic resonance
electron transfer

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4 : 9,10-bis(dicarboximide) Donor-Acceptor Dyads. / Huang, Guan Jhih; Harris, Michelle A.; Krzyaniak, Matthew D.; Margulies, Eric A.; Dyar, Scott M.; Lindquist, Rebecca J.; Wu, Yilei; Roznyatovskiy, Vladimir V.; Wu, Yi Lin; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of Physical Chemistry B, Vol. 120, No. 4, 04.02.2016, p. 756-765.

Research output: Contribution to journalArticle

Huang, GJ, Harris, MA, Krzyaniak, MD, Margulies, EA, Dyar, SM, Lindquist, RJ, Wu, Y, Roznyatovskiy, VV, Wu, YL, Young, RM & Wasielewski, MR 2016, 'Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4: 9,10-bis(dicarboximide) Donor-Acceptor Dyads', Journal of Physical Chemistry B, vol. 120, no. 4, pp. 756-765. https://doi.org/10.1021/acs.jpcb.5b10806
Huang, Guan Jhih ; Harris, Michelle A. ; Krzyaniak, Matthew D. ; Margulies, Eric A. ; Dyar, Scott M. ; Lindquist, Rebecca J. ; Wu, Yilei ; Roznyatovskiy, Vladimir V. ; Wu, Yi Lin ; Young, Ryan M. ; Wasielewski, Michael R. / Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4 : 9,10-bis(dicarboximide) Donor-Acceptor Dyads. In: Journal of Physical Chemistry B. 2016 ; Vol. 120, No. 4. pp. 756-765.
@article{de1f54d4558a41a9b732a4b5573b71d4,
title = "Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4: 9,10-bis(dicarboximide) Donor-Acceptor Dyads",
abstract = "Connecting electron donors and acceptors to a benzene ring in a meta or para relationship results in quantum interference effects that can strongly influence charge separation (CS) and charge recombination (CR) processes in these systems. We report on the energy and electron transfer behavior of chlorophyll-based para- and meta-linked donor-bridge-acceptor (D-B-A) dyads, where the semisynthetic chlorophyll a derivative, zinc methyl 3-ethyl-pyrochlorophyllide a (D), is covalently attached at its 20-position to the para position of one phenyl of diphenylacetylene (B). The meta or para position of the phenyl in B distal to the donor is in turn attached to perylene-3,4:9,10-bis(dicarboximide) (PDI) (A). Photoexcitation of the D-B-A dyads produces long-lived radical ion pairs D•+-B-A•-, which recombine to the ground state and to both 3∗D-B-A and D-B-3∗A. Time-resolved optical and electron paramagnetic resonance spectroscopies were used to monitor the charge transfer and triplet energy transfer (TEnT) processes. At longer times, TEnT occurs from 3∗D-B-A to D-B-3∗A. Surprisingly, the D-B-A molecules linked via the meta linkage exhibit faster CS, CR, and TEnT rates than do those with the para linkage in contrast to most other meta/para-linked D-B-A molecules previously examined.",
author = "Huang, {Guan Jhih} and Harris, {Michelle A.} and Krzyaniak, {Matthew D.} and Margulies, {Eric A.} and Dyar, {Scott M.} and Lindquist, {Rebecca J.} and Yilei Wu and Roznyatovskiy, {Vladimir V.} and Wu, {Yi Lin} and Young, {Ryan M.} and Wasielewski, {Michael R}",
year = "2016",
month = "2",
day = "4",
doi = "10.1021/acs.jpcb.5b10806",
language = "English",
volume = "120",
pages = "756--765",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Photoinduced Charge and Energy Transfer within meta- and para-Linked Chlorophyll a-Perylene-3,4

T2 - 9,10-bis(dicarboximide) Donor-Acceptor Dyads

AU - Huang, Guan Jhih

AU - Harris, Michelle A.

AU - Krzyaniak, Matthew D.

AU - Margulies, Eric A.

AU - Dyar, Scott M.

AU - Lindquist, Rebecca J.

AU - Wu, Yilei

AU - Roznyatovskiy, Vladimir V.

AU - Wu, Yi Lin

AU - Young, Ryan M.

AU - Wasielewski, Michael R

PY - 2016/2/4

Y1 - 2016/2/4

N2 - Connecting electron donors and acceptors to a benzene ring in a meta or para relationship results in quantum interference effects that can strongly influence charge separation (CS) and charge recombination (CR) processes in these systems. We report on the energy and electron transfer behavior of chlorophyll-based para- and meta-linked donor-bridge-acceptor (D-B-A) dyads, where the semisynthetic chlorophyll a derivative, zinc methyl 3-ethyl-pyrochlorophyllide a (D), is covalently attached at its 20-position to the para position of one phenyl of diphenylacetylene (B). The meta or para position of the phenyl in B distal to the donor is in turn attached to perylene-3,4:9,10-bis(dicarboximide) (PDI) (A). Photoexcitation of the D-B-A dyads produces long-lived radical ion pairs D•+-B-A•-, which recombine to the ground state and to both 3∗D-B-A and D-B-3∗A. Time-resolved optical and electron paramagnetic resonance spectroscopies were used to monitor the charge transfer and triplet energy transfer (TEnT) processes. At longer times, TEnT occurs from 3∗D-B-A to D-B-3∗A. Surprisingly, the D-B-A molecules linked via the meta linkage exhibit faster CS, CR, and TEnT rates than do those with the para linkage in contrast to most other meta/para-linked D-B-A molecules previously examined.

AB - Connecting electron donors and acceptors to a benzene ring in a meta or para relationship results in quantum interference effects that can strongly influence charge separation (CS) and charge recombination (CR) processes in these systems. We report on the energy and electron transfer behavior of chlorophyll-based para- and meta-linked donor-bridge-acceptor (D-B-A) dyads, where the semisynthetic chlorophyll a derivative, zinc methyl 3-ethyl-pyrochlorophyllide a (D), is covalently attached at its 20-position to the para position of one phenyl of diphenylacetylene (B). The meta or para position of the phenyl in B distal to the donor is in turn attached to perylene-3,4:9,10-bis(dicarboximide) (PDI) (A). Photoexcitation of the D-B-A dyads produces long-lived radical ion pairs D•+-B-A•-, which recombine to the ground state and to both 3∗D-B-A and D-B-3∗A. Time-resolved optical and electron paramagnetic resonance spectroscopies were used to monitor the charge transfer and triplet energy transfer (TEnT) processes. At longer times, TEnT occurs from 3∗D-B-A to D-B-3∗A. Surprisingly, the D-B-A molecules linked via the meta linkage exhibit faster CS, CR, and TEnT rates than do those with the para linkage in contrast to most other meta/para-linked D-B-A molecules previously examined.

UR - http://www.scopus.com/inward/record.url?scp=84957582092&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84957582092&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcb.5b10806

DO - 10.1021/acs.jpcb.5b10806

M3 - Article

VL - 120

SP - 756

EP - 765

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 4

ER -