1. Isotropic Three-Dimensional Molecular Conductor Based on the Coronene Radical Cation.
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Yoshida, Yukihiro, Maesato, Mitsuhiko, Kumagai, Yoshihide, Mizuno, Motohiro, Isomura, Kazuhide, Kishida, Hideo, Izumi, Masanari, Kubozono, Yoshihiro, Otsuka, Akihiro, Yamochi, Hideki, Saito, Gunzi, Kirakci, Kaplan, Cordier, Stéphane, and Perrin, Christiane
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ELECTRICAL conductors ,CATIONS ,RADICALS (Chemistry) ,POLYCYCLIC aromatic hydrocarbons ,MOLYBDENUM ,CARBON-hydrogen bonds - Abstract
In this study, we obtained the first cation radical solid of a highly symmetric ( D
6 h ) polyaromatic hydrocarbon, coronene, by electrooxidation. The (coronene)3 Mo6 Cl14 salt, which is formed with an Oh -symmetric molybdenum cluster unit Mo6 Cl14 2- , has an isotropic cubic structure with Pm $\bar {3}$ m symmetry. The presence of two orientations for the coronene molecules related by an in-plane 90° rotation (merohedral disorder) allows for fourfold symmetry along the <100> direction. The disorder has dynamic features because2 H NMR spectroscopic studies revealed that the coronene molecules undergo an in-plane flipping motion. The observation of two motional sites with significantly different rotational rates (300 Hz and 5 MHz at 103 K) in an approximate 2:1 ratio appears to be consistent with the splitting of a Raman-active A1g mode, confirming a random charge-disproportionated state instead of a uniform partially-charged state. The slower- and faster-rotating species are assigned to charge-rich and charge-poor coronenes, respectively, with respect to C-H ···Cl hydrogen bonds with neighboring Mo6 Cl14 2- cluster units. The electrical conductivity of the salt is rather high but is well-described by a three-dimensional (3D) variable-range hopping mechanism, which is possibly associated with the random charge disproportionation. These results provide a significant step forward in developing an isotropic 3D π-conducting system composed of planar π-conjugated molecules. [ABSTRACT FROM AUTHOR]- Published
- 2014
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