%0 Journal Article
%A Wielopolski, Mateusz
%A Molina Ontoria, Agustín
%A Schubert, Christina
%A Margraf. Johannes T.
%A Krokos, Evangelos
%A Kirschner, Johannes
%A Gouloumis, Andreas
%A Clark, Timothy
%A Guldi, Dirk M.
%A Martín León, Nazario
%T Blending through-space and through-bond π–π-coupling in [2,2′]-paracyclophane-oligophenylenevinylene molecular wires
%D 2013
%@ 0002-7863
%@ 1520-5126
%U https://hdl.handle.net/20.500.14352/115116
%X A series of ZnP-pCp-oPPV-C60 conjugates covalently connected through [2,2′]-paracyclophane-oligophenylenevinylene (pCp-oPPV) bridges containing one, two, and three [2,2′]-paracyclophanes (pCps) has been prepared in multistep synthetic procedures involving Horner-Wadsworth-Emmons olefination reactions and/or Heck type Pd-catalyzed reactions. Molecular modeling suggests that charge transfer is effectively mediated by the pCp-oPPVs through a predominant hole-transfer mechanism. Photophysical investigation supports molecular modeling and reveals two major trends. On one hand, C 60 excitation of 1, 2, and 3 leads exclusively to charge transfer between pCp and C60 to afford a ZnP-(pCp-oPPV)•+- C60•- radical ion pair state without giving rise to a subsequent charge shift to yield the ZnP•+-pCp-oPPV-C 60•- radical ion pair state. On the other hand, ZnP excitation of 1, 2, and 3 results in a rather slow charge transfer between ZnP and C60, after which the ZnP•+-pCp-oPPV-C 60•- radical ion pair state evolves. In temperature-dependent ZnP fluorescence experiments, which were performed in the temperature range from 273 to 338 K, two domains are discernible: low and high temperature behaviors. In the low temperature range (i.e., below 30 C) the rate constants do not change, suggesting that a superexchange mechanism is the modus operandi. In the high temperature range (i.e., >30 C) the rate constants increase. Moreover, we find rather strong distance dependence for 1 and 2 and weak distance dependence for 2 and 3. A damping factor of 0.145 Å-1 is derived for the former pair and 0.012 Å-1 for the latter.
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