Helically Twisted Nanoribbons Based on Emissive Near-Infrared Responsive Quaterrylene Bisimides

• Published in: Journal of the American Chemical Society Vol. 144; no. 23; pp. 10507 - 10514
• Main Authors: Mahlmeister, Bernhard, Mahl, Magnus, Reichelt, Helmut, Shoyama, Kazutaka, Stolte, Matthias, Würthner, Frank
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.06.2022; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; NANOGRAPHENE; DYES
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.2c02947

Graphene nanoribbons (GNRs) have the potential for next-generation functional devices. So far, GNRs with defined stereochemistry are rarely reported in literature and their optical response is usually bound to the ultraviolet or visible spectral region, while covering the near-infrared (NIR) regime is still challenging. Herein, we report two novel quaterrylene bisimides with either one- or twofold-twisted π-backbones enabled by the steric congestion of a fourfold bay arylation leading to an end-to-end twist of up to 76°. The strong interlocking effect of the π-stacked aryl substituents introduces a rigidification of the chromophore unambiguously proven by single-crystal X-ray analysis. This leads to unexpectedly strong NIR emissions at 862 and 903 nm with quantum yields of 1.5 and 0.9%, respectively, further ensuring high solubility as well as resolvable and highly stable atropo-enantiomers. Circular dichroism spectroscopy of these enantiopure chiral compounds reveals a strong Cotton effect Δε of up to 67 M–1 cm–1 centered far in the NIR region at 849 nm.