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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...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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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 |
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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 |
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