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O‐Doped Nanographenes: A Pyrano/Pyrylium Route Towards Semiconducting Cationic Mixed‐Valence Complexes
Author(s) -
Ðorđević Luka,
Valentini Cataldo,
Demitri Nicola,
Mézière Cécile,
Allain Magali,
Sallé Marc,
Folli Andrea,
Murphy Damien,
MañasValero Samuel,
Coronado Eugenio,
Bonifazi Davide
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914025
Subject(s) - electron paramagnetic resonance , cationic polymerization , valence (chemistry) , heteroatom , delocalized electron , doping , stacking , pyrene , chemistry , photochemistry , organic electronics , materials science , chemical physics , crystallography , organic chemistry , nuclear magnetic resonance , alkyl , optoelectronics , physics , transistor , voltage , quantum mechanics
Herein we report an efficient synthesis to prepare O‐doped nanographenes derived from the π‐extension of pyrene. The derivatives are highly fluorescent and feature low oxidation potentials. Using electrooxidation, crystals of cationic mixed‐valence (MV) complexes were grown in which the organic salts organize into face‐to‐face π‐stacks, a favorable solid‐state arrangement for organic electronics. Variable‐temperature electron paramagnetic resonance (EPR) measurements and relaxation studies suggest a strong electron delocalization along the longitudinal axis of the columnar π‐stacking architectures. Electric measurements of single crystals of the MV salts show a semiconducting behavior with a remarkably high conductivity at room temperature. These findings support the notion that π‐extension of heteroatom‐doped polycyclic aromatic hydrocarbons is an attractive approach to fabricate nanographenes with a broad spectrum of semiconducting properties and high charge mobilities.