Cargando…

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

[Image: see text] 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...

Descripción completa

Detalles Bibliográficos
Autores principales: Penty, Samuel E., Zwijnenburg, Martijn A., Orton, Georgia R. F., Stachelek, Patrycja, Pal, Robert, Xie, Yujie, Griffin, Sarah L., Barendt, Timothy A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9348826/
https://www.ncbi.nlm.nih.gov/pubmed/35763425
http://dx.doi.org/10.1021/jacs.2c03531
_version_ 1784761998228062208
author Penty, Samuel E.
Zwijnenburg, Martijn A.
Orton, Georgia R. F.
Stachelek, Patrycja
Pal, Robert
Xie, Yujie
Griffin, Sarah L.
Barendt, Timothy A.
author_facet Penty, Samuel E.
Zwijnenburg, Martijn A.
Orton, Georgia R. F.
Stachelek, Patrycja
Pal, Robert
Xie, Yujie
Griffin, Sarah L.
Barendt, Timothy A.
author_sort Penty, Samuel E.
collection PubMed
description [Image: see text] 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.
format Online
Article
Text
id pubmed-9348826
institution National Center for Biotechnology Information
language English
publishDate 2022
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-93488262022-08-04 The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle Penty, Samuel E. Zwijnenburg, Martijn A. Orton, Georgia R. F. Stachelek, Patrycja Pal, Robert Xie, Yujie Griffin, Sarah L. Barendt, Timothy A. J Am Chem Soc [Image: see text] 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. American Chemical Society 2022-06-28 2022-07-13 /pmc/articles/PMC9348826/ /pubmed/35763425 http://dx.doi.org/10.1021/jacs.2c03531 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Penty, Samuel E.
Zwijnenburg, Martijn A.
Orton, Georgia R. F.
Stachelek, Patrycja
Pal, Robert
Xie, Yujie
Griffin, Sarah L.
Barendt, Timothy A.
The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
title The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
title_full The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
title_fullStr The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
title_full_unstemmed The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
title_short The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle
title_sort the pink box: exclusive homochiral aromatic stacking in a bis-perylene diimide macrocycle
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9348826/
https://www.ncbi.nlm.nih.gov/pubmed/35763425
http://dx.doi.org/10.1021/jacs.2c03531
work_keys_str_mv AT pentysamuele thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT zwijnenburgmartijna thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT ortongeorgiarf thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT stachelekpatrycja thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT palrobert thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT xieyujie thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT griffinsarahl thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle
AT barendttimothya thepinkboxexclusivehomochiralaromaticstackinginabisperylenediimidemacrocycle