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Charge-Transfer Localization in Molecularly Doped Thiophene-Based Donor Polymers

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Institut für Physik, Humboldt University Berlin, Newtonstrasse 15, 12489 Berlin, Germany
Institute of Physics and Astronomy, University of Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam, Germany
§ School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332-0400
Fraunhofer Institute for Applied Polymer Research, Geiselbergstrasse 69, 14476 Potsdam, Germany
*To whom correspondence should be addressed. E-mail: [email protected]
Cite this: J. Phys. Chem. Lett. 2010, 1, 13, 2037–2041
Publication Date (Web):June 16, 2010
Copyright © 2010 American Chemical Society

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    Abstract Image

    We provide evidence for highly localized charge-transfer complex formation between a series of thiophenetetrafluorobenzene donor copolymers and the molecular acceptor tetrafluorotetracyanoquinodimethane (F4TCNQ). Infrared absorption spectra of diagnostic vibrational bands in conjunction with theoretical modeling show that one acceptor molecule undergoes charge transfer with a quaterthiophene segment of the polymers, irrespective of the macroscopic polymer ionization energy and acceptor concentration in thin films. The interaction is thus determined by the “local ionization potential” of quaterthiophene. Consequently, using materials parameters determined on a macroscopic length scale as a guideline for making new charge-transfer complex materials for high electrical conductivity turns out to be oversimplified, and a reliable material design must take into account property variations on the nm scale as well.

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    Experimental and preparation details, full-range IR spectra, theoretically modeled charge-transfer complexes, and vibrational frequencies/intensities. This material is available free of charge via the Internet at

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