Ultrafast electron transfer reactions initiated by excited CT states of push-pull perylenes

Scott E. Miller, Yongyu Zhao, Richard D Schaller, Viviana Mulloni, Eric M. Just, Robert C. Johnson, Michael R Wasielewski

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Two new chromophores that absorb in the visible spectrum, the 9-(N-pyrrolidinyl)- and 9-(N-piperidinyl)perylene-3,4-dicarboximides, 5PMI and 6PMI, respectively, were synthesized and shown to possess lowest excited singlet states with about 70% charge transfer (CT) character. Changing the ring size of the cyclic amine from 5 to 6 significantly changes the energies of the CT states, as well as the redox potentials of the chromophores. These chromophores were linked to pyromellitimide (PI) and 1,8:4,5-naphthalenediimide (NI) electron acceptors using a single N-N bond between their respective imides to yield the corresponding donor-acceptor dyads 5PMI-PI, 5PMI-NI, 6PMI-PI, and 6PMI-NI. The donors and acceptors in these molecules are positioned relative to one another in a rod-like arrangement at fixed distances and restricted orientations. The rates of charge separation and recombination were measured using transient absorption spectroscopy. These chromophores were also used to prepare rigid donor-acceptor triads 5PMI-PI-NI and 6PMI-PI-NI, which display one- or two-step electron transfer mechanisms that depend on solvent polarity. These compounds exhibit a broad range of structure and media driven changes in electron transfer mechanism.

Original languageEnglish
Pages (from-to)167-183
Number of pages17
JournalChemical Physics
Volume275
Issue number1-3
DOIs
Publication statusPublished - Jan 1 2002

Fingerprint

chromophores
Charge transfer
Chromophores
electron transfer
charge transfer
Electrons
Perylene
imides
Imides
polarization (charge separation)
visible spectrum
polarity
amines
absorption spectroscopy
Absorption spectroscopy
rods
Excited states
Amines
naphthalenediimide
rings

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Ultrafast electron transfer reactions initiated by excited CT states of push-pull perylenes. / Miller, Scott E.; Zhao, Yongyu; Schaller, Richard D; Mulloni, Viviana; Just, Eric M.; Johnson, Robert C.; Wasielewski, Michael R.

In: Chemical Physics, Vol. 275, No. 1-3, 01.01.2002, p. 167-183.

Research output: Contribution to journalArticle

Miller, Scott E. ; Zhao, Yongyu ; Schaller, Richard D ; Mulloni, Viviana ; Just, Eric M. ; Johnson, Robert C. ; Wasielewski, Michael R. / Ultrafast electron transfer reactions initiated by excited CT states of push-pull perylenes. In: Chemical Physics. 2002 ; Vol. 275, No. 1-3. pp. 167-183.
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