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

13 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

ASJC Scopus subject areas

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

Cite this

Huang, G. J., Harris, M. A., Krzyaniak, M. D., Margulies, E. A., Dyar, S. M., Lindquist, R. J., Wu, Y., Roznyatovskiy, V. V., Wu, Y. L., Young, R. M., & Wasielewski, M. R. (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, 120(4), 756-765. https://doi.org/10.1021/acs.jpcb.5b10806