Open AccessThe Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
Author(s) -
Samuel E Penty,
Martijn A. Zwijnenburg,
Georgia R. F. Orton,
Patrycja Stachelek,
Róbert Pál,
Yujie Xie,
Sarah L. Griffin,
Timothy A. Barendt
Publication year - 2022
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.2c03531
Subject(s) - chemistry , stacking , perylene , diimide , intramolecular force , supramolecular chemistry , enantiomer , molecule , crystallography , chirality (physics) , stereochemistry , crystal structure , organic chemistry , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
This work showcases chiral complementarity in aromatic stacking interactions as an effective tool to optimize the chiroptical and electrochemical properties of perylene diimides (PDIs). PDIs are a notable class of robust dye molecules and their rich photo- and electrochemistry and potential chirality make them ideal organic building blocks for chiral optoelectronic materials. By exploiting the new bay connectivity of twisted PDIs, a dynamic bis-PDI macrocycle (the "Pink Box") is realized in which homochiral PDI-PDI π-π stacking interactions are switched on exclusively. Using a range of experimental and computational techniques, we uncover three important implications of the macrocycle's chiral complementarity for PDI optoelectronics. First, the homochiral intramolecular π-π interactions anchor the twisted PDI units, yielding enantiomers with half-lives extended over 400-fold, from minutes to days (in solution) or years (in the solid state). Second, homochiral H-type aggregation affords the macrocycle red-shifted circularly polarized luminescence and one of the highest dissymmetry factors of any small organic molecule in solution ( g lum = 10 -2 at 675 nm). Finally, excellent through-space PDI-PDI π-orbital overlap stabilizes PDI reduced states, akin to covalent functionalization with electron-withdrawing groups.