Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes.
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.
Department of Physical Chemistry, University of Málaga , Campus de Teatinos s/n, Málaga 29071, Spain.
José L
JL
Zafra
IMDEA-Nanociencia, C/Faraday 9, Ciudad Universitaria de Cantoblanco , 28049 Madrid, Spain.
Agustín
0000-0003-3924-7150
A
Molina Ontoria
Department of Physical Chemistry, University of Málaga , Campus de Teatinos s/n, Málaga 29071, Spain.
Paula
P
Mayorga Burrezo
Miriam
0000-0001-7056-7158
M
Peña-Alvarez
Advanced Materials Engineering and Modelling Group, Faculty of Chemistry, Wroclaw University of Science and Technology , 50370 Wroclaw, Poland.
Marek
0000-0002-5404-2455
M
Samoc
Advanced Materials Engineering and Modelling Group, Faculty of Chemistry, Wroclaw University of Science and Technology , 50370 Wroclaw, Poland.
Janusz
J
Szeremeta
Department of Physical Chemistry, University of Málaga , Campus de Teatinos s/n, Málaga 29071, Spain.
Francisco J
0000-0002-8149-9143
FJ
Ramírez
Division of Science and Mathematics, University of Minnesota , Morris, Minnesota 56267, United States.
Matthew D
MD
Lovander
Division of Science and Mathematics, University of Minnesota , Morris, Minnesota 56267, United States.
Christopher J
CJ
Droske
Division of Science and Mathematics, University of Minnesota , Morris, Minnesota 56267, United States.
Ted M
TM
Pappenfus
Department of Chemistry, University of Texas at El Paso , El Paso, Texas 79968, United States.
Luis
0000-0003-1107-9423
L
Echegoyen
Department of Physical Chemistry, University of Málaga , Campus de Teatinos s/n, Málaga 29071, Spain.
Juan T
JT
López Navarrete
IMDEA-Nanociencia, C/Faraday 9, Ciudad Universitaria de Cantoblanco , 28049 Madrid, Spain.
Nazario
0000-0002-5355-1477
N
Martín
Department of Physical Chemistry, University of Málaga , Campus de Teatinos s/n, Málaga 29071, Spain.
Juan
0000-0003-0373-1303
J
Casado