TY - JOUR
T1 - Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes
AU - Zafra, Jose L.
AU - Ontoria, Augustin Molina
AU - Burrezo, Paula Mayorga
AU - Pena Alvarez, Miriam
AU - Samoc, Marek
AU - Szeremeta, Janusz
AU - Ramirez, Francisco J.
AU - Lovander, Matthew D.
AU - Droske, Christopher J.
AU - Pappenfus, Ted M.
AU - Echegoyen, Luis
AU - Lopez Navarrete, Juan T
AU - Martin, Nazario
AU - Casado, Juan
PY - 2017/3/1
Y1 - 2017/3/1
N2 - 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.
AB - 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.
U2 - 10.1021/jacs.6b12520
DO - 10.1021/jacs.6b12520
M3 - Article
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
ER -