TY  - JOUR
AU  - Mahlmeister, Bernhard
AU  - Schembri, Tim
AU  - Stepanenko, Vladimir
AU  - Shoyama, Kazutaka
AU  - Stolte, Matthias
AU  - Wuerthner, Frank
TI  - Enantiopure J-Aggregate of Quaterrylene Bisimides for Strong Chiroptical NIR-Response
JO  - Journal of the American Chemical Society
VL  - 145
IS  - 24
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2023-05334
SP  - 13302 - 13311
PY  - 2023
AB  - Chiral polycyclic aromatic hydrocarbons can be tailored for next-generation photonic materials by carefully designing their molecular as well as supramolecular architectures. Hence, excitonic coupling can boost the chiroptical response in extended aggregates but is still challenging to achieve by pure self-assembly. Whereas most reports on these potential materials cover the UV and visible spectral range, systems in the near infrared (NIR) are underdeveloped. We report a new quaterrylene bisimide derivative with a conformationally stable twisted π-backbone enabled by the sterical congestion of a fourfold bay-arylation. Rendering the π-subplanes accessible by small imide substituents allows for a slip-stacked chiral arrangement by kinetic self-assembly in low polarity solvents. The well dispersed solid-state aggregate reveals a sharp optical signature of strong J-type excitonic coupling in both absorption (897 nm) and emission (912 nm) far in the NIR region and reaches absorption dissymmetry factors up to 1.1 × 10<sup>–2</sup>. The structural elucidation was achieved by atomic force microscopy and single-crystal X-ray analysis which we combined to derive a structural model of a fourfold stranded enantiopure superhelix. We could deduce that the role of phenyl substituents is not only granting stable axial chirality but also guiding the chromophore into a chiral supramolecular arrangement needed for strong excitonic chirality.
LB  - PUB:(DE-HGF)16
C6  - 37285519
UR  - <Go to ISI:>//WOS:001008513400001
DO  - DOI:10.1021/jacs.3c03367
UR  - https://bib-pubdb1.desy.de/record/593234
ER  -