Litcius/Paper detail

Transformation of Crowded Oligoarylene into Perylene‐Cored Chiral Nanographene by Sequential Oxidative Cyclization and 1,2‐Phenyl Migration

Jinghao Wang, Chengshuo Shen, Guoli Zhang, Fuwei Gan, Yongle Ding, Huibin Qiu

2021Angewandte Chemie International Edition48 citationsDOI

Abstract

Abstract Synthetic innovation for constructing sophisticated nanographenes is of fundamental significance for a variety of advanced applications. Herein, we report a distinctive method to prepare π‐extended chiral nanographenes with 29 benzenoid rings and two helical breaches from a highly crowded perylene‐cored oligoarylene precursor. Under Scholl's conditions, the reaction predominantly involves the regioselective and sequential cyclization in the peri ‐ and bay regions of the perylene core, and the complanation of the 1‐phenyl[5]helicene intermediate module via 1,2‐phenyl migration. The resulting chiral nanographenes are configurationally stable at 180 °C due to the high diastereomerization barriers of ca. 45 kcal mol −1 . These molecules also possess globally delocalized π‐systems with low HOMO/LUMO gaps, leading to nearly panchromatic absorption, intensive electronic circular dichroism signals and deep‐red circularly polarized luminescence.

Topics & Concepts

PeryleneDelocalized electronHeliceneCircular dichroismLuminescenceRegioselectivityMoleculePhotochemistryHOMO/LUMOMaterials scienceChemistryStereochemistryCrystallographyOrganic chemistryOptoelectronicsCatalysisSynthesis and Properties of Aromatic CompoundsLuminescence and Fluorescent MaterialsGraphene research and applications