Published on Web 06/09/2009
Toward an n-Type Molecular Wire: Electron Hopping within
Linearly Linked Perylenediimide Oligomers
Thea M. Wilson,† Michael J. Tauber,‡ and Michael R. Wasielewski*,†
Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center,
Northwestern UniVersity, EVanston, Illinois 60208-3113, and Department of Chemistry and
Biochemistry, UniVersity of California San Diego, La Jolla, California 92093-0314
Received March 22, 2009; E-mail: m-wasielewski@northwestern.edu
Abstract: A series of linearly linked perylenediimide (PDI) dimers and trimers were synthesized in which
the PDI π systems are nearly orthogonal. These oligomers and several model compounds were singly
reduced, and intramolecular electron hopping between the PDI molecules was probed by electron
paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy. When
the functional groups attached to the ends of the oligomers were chosen to make each PDI molecule
electronically equivalent, the single electron hops between the PDI molecules with rates that significantly
exceed 107 s-1. Rapid electron hopping between pairs of PDI molecules having orthogonal π systems is
unexpected and may expand the possible design motifs for organic electronic materials based on PDI.
is both photochemically and thermally stable19 and can be easily
modified at its imide nitrogens and its 1, 6, 7, and 12 positions.
Introduction
Efficient charge transport among neighboring molecules is a
requirement for the successful implementation of organic
electronics, which have gained popularity because of their
potential low-cost, ease of processability, and mechanical
flexibility. Perylene-3,4:9,10-bis(dicarboximide) (PDI) and its
derivatives have attracted significant interest as active materials
for light harvesting,1-4 photovoltaics,5-12 and studies of basic
photoinduced charge and energy transfer processes.13-18 PDI
Modifications at these positions tune the electronic properties
of PDI, resulting in derivatives that absorb light from the near-
ultraviolet to the near-infrared region of the spectrum and that
are either good electron acceptors20 or donors.21 PDI also
demonstrates the ability to self-assemble in solution via
hydrophobic/hydrophilic interactions as well as by π-π stack-
ing, a phenomenon which has been extensively studied in a
variety of self-assembled, π-stacked PDI systems.22-32 We have
† Northwestern University.
‡ University of California, San Diego.
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10.1021/ja902258g CCC: $40.75 2009 American Chemical Society