Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

José L. Zafra, Agustín Molina Ontoria, Paula Mayorga Burrezo, Miriam Peña-Alvarez, Marek Samoc, Janusz Szeremeta, Francisco J. Ramírez, Matthew D. Lovander, Christopher J. Droske, Ted M. Pappenfus, Luis Echegoyen, Juan T. López Navarrete, Nazario Martín, Juan Casado

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33 Scopus citations

Abstract

New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

Original languageEnglish (US)
Pages (from-to)3095-3105
Number of pages11
JournalJournal of the American Chemical Society
Volume139
Issue number8
DOIs
StatePublished - Mar 1 2017

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© 2017 American Chemical Society.

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