The Precise Synthesis of Phenylene-Extended Cyclic Hexa-peri-hexabenzocoronenes from Polyarylated [n]Cycloparaphenylenes by the Scholl Reaction

• Published in: Angewandte Chemie International Edition Vol. 54; no. 35; pp. 10341 - 10346
• Main Authors: Quernheim, Martin, Golling, Florian E., Zhang, Wen, Wagner, Manfred, Räder, Hans-Joachim, Nishiuchi, Tomohiko, Müllen, Klaus
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 24.08.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Benzene; Carbon nanotubes; Chemistry; Chemistry, Multidisciplinary; cycloparaphenylene; macrocycles; Nanotechnology; Nanotubes; Physical Sciences; polycyclic aromatic hydrocarbons; Scholl reaction; Science & Technology; Synthesis; Trimers; ELECTRONIC-PROPERTIES; GRAPHENE NANORIBBONS; CRYSTAL-STRUCTURE; Scholl reaction; polycyclic aromatic hydrocarbons; WALLED CARBON NANOTUBES; cycloparaphenylene; carbon nanotubes; FLUORESCENCE; macrocycles; CYCLOPARAPHENYLENES; SELECTIVE SYNTHESIS; EFFICIENT; HYDROCARBON; BOTTOM-UP SYNTHESIS
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201500392

The longitudinal extension of cycloparaphenylenes (CPP) towards ultrashort carbon nanotubes (CNTs) is essential for the solution based bottom‐up synthesis of CNTs. Herein, the longitudinal extension of the CPP skeleton by the introduction of hexaphenylbenzene units towards polyarylated [n]CPPs is described. Further, the applicability of the Scholl reaction to selectively form graphenic sidewalls is demonstrated. The ring size and substitution patterns of the polyarylated [n]CPPs were varied to overcome strain‐induced side reactions during the oxidative cyclodehydrogenation and cyclic para‐hexa‐peri‐hexabenzocoronene trimers ([3]CHBCs) were selectively obtained. This concept is envisioned as an access to ultrashort carbon nanotubes subject to the condition that further benzene rings with the right connectivity will be inserted. All that it′s cutout to be: Polyarylated [n]cycloparaphenylenes are intermediates on the way to ultra‐short carbon nanotubes (CNT). Different polyarylated [n]CPPs can be prepared and their oxidative cyclodehydrogenation leads to CPPs that are cutouts from CNTs.