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

Jose L. Zafra, Augustin Molina Ontoria, Paula Mayorga Burrezo, Miriam Pena Alvarez, Marek Samoc, Janusz Szeremeta, Francisco J. Ramirez, Matthew D. Lovander, Christopher J. Droske, Ted M. Pappenfus, Luis Echegoyen, Juan T Lopez Navarrete, Nazario Martin, Juan Casado

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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
JournalJournal of the American Chemical Society
Early online date21 Feb 2017
DOIs
Publication statusPublished - 1 Mar 2017

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