O‐Doped Nanographenes: A Pyrano/Pyrylium Route Towards Semiconducting Cationic Mixed‐Valence Complexes. (24th January 2020)

• Record Type: Journal Article
• Authors: Ðorđević, Luka; Valentini, Cataldo; Demitri, Nicola; Mézière, Cécile; Allain, Magali; Sallé, Marc; Folli, Andrea; Murphy, Damien; Mañas‐Valero, Samuel; Coronado, Eugenio; Bonifazi, Davide
• Is Part Of: Angewandte Chemie. Volume 132:Number 10(2020)
• Page Start: 4135
• Page End: 4143
• Publication Date: 2020-01-24
• Subjects: Elektrokristallisierung -- Elektronenspinresonanz -- Heteroatomdotierung -- Molekulare Graphene -- Polycyclische aromatische Kohlenwasserstoffe; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201914025
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : Ein bisschen O muss sein : O‐dotierte, aus der π‐Systemerweiterung von Pyren abgeleitete Nanographene werden vorgestellt. Die Verbindungen sind stark fluoreszierend und besitzen niedrige Oxidationspotentiale. Elektrische Messungen der Einkristalle von Mischvalenzsalzen zeigen ein Halbleiter‐Verhalten mit bemerkenswert hoher Leitfähigkeit bei Raumtemperatur.