Synthesis and Chiroptical Activity of π-Expanded Electron-Rich Heterohelicenes Based on the 1,4-Dihydropyrrolo[3,2-b]pyrrole Core

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dc.contributor.authorKusy, Damian
dc.contributor.authorGórski, Krzysztof
dc.contributor.authorBertocchi, Francesco
dc.contributor.authorGalli, Matteo
dc.contributor.authorVanthuyne, Nicolas
dc.contributor.authorTerenziani, Francesca
dc.contributor.authorGryko, Daniel T.
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciences
dc.contributor.organizationDepartment of Chemistry, Life Sciences and Environmental Sustainability, University of Parma
dc.contributor.organizationAix Marseille Univ, CNRS, France
dc.date.accessioned2025-08-20T12:06:58Z
dc.date.available2025-08-20T12:06:58Z
dc.date.issued2025
dc.description.abstractHerein, we report the synthesis and chiroptical characteristics of the first (double) helicenes possessing the 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) moiety as their central core. We have developed a three-step synthesis with 6π-electrocyclization accompanied by HBr elimination as its key step. We found that, whereas for smaller peripheral arms double 6π-electrocyclization occurs smoothly forming a double helicene, in the case of longer polycyclic aromatic hydrocarbons the reaction becomes less efficient and mono-helicenes are the only products. The electron density distribution analysis of LUMO explains the different regioselectivity of 6π-electrocyclization. The synthesized heterohelicenes are characterized by greenish-blue emission, distinct solvatofluorochromism and good fluorescence quantum yields (up to 42 %). Moreover, the chiroptical measurements reveal that unsymmetrical double heterohelicene exhibits excellent circularly polarized luminescence brightness (BCPL) reaching 30 M-1 cm-1. The combined experimental and computational study has revealed that a charge-transfer state is responsible for the observed emission (hence the solvatochromism), while low-energy absorption derives from multiple transitions.en
dc.description.sponsorshipEuropean Union's Horizon2020 research and innovation programme under the Marie Skłodowska-Curie grant agreements No 101007804 (Micro4Nano) and No 860762; Polish National Science Centre, Poland (OPUS 2020/37/B/ST4/00017); COMP-HUB and COMP-R initiatives, funded by the “Departments of Excellence” program of the Italian Ministry for University and Research (MIUR, 2018-2022 and MUR, 2023-2027).
dc.identifier.citationChem. Eur. J. 2025, 31, e202404632 (1 of 8) // https://doi.org/10.1002/chem.202404632
dc.identifier.doi10.1002/chem.202404632
dc.identifier.issn0947-6539
dc.identifier.issn1521-3765
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/26057
dc.language.isoen
dc.publisherWiley-VCH GmbH
dc.rightsUznanie autorstwa-Użycie niekomercyjne 4.0 Międzynarodoween
dc.rights.urihttp://creativecommons.org/licenses/by-nc/4.0/
dc.sourceChemistry – A European Journal
dc.subjectheliceneen
dc.subjectdyes/pigmentsen
dc.subjectpyrroleen
dc.subjectfluorescenceen
dc.subjectcircularly polarized luminescenceen
dc.titleSynthesis and Chiroptical Activity of π-Expanded Electron-Rich Heterohelicenes Based on the 1,4-Dihydropyrrolo[3,2-b]pyrrole Coreen
dc.typearticle
dc.type.versionpublishedVersion
person.identifier.orcidKusy, Damian [0000-0002-0643-3478]
person.identifier.orcidGórski, Krzysztof [0000-0002-6439-2651]
person.identifier.orcidBertocchi, Francesco [0000-0002-6290-9119]
person.identifier.orcidVanthuyne, Nicolas [0000-0003-2598-7940]
person.identifier.orcidTerenziani, Francesca [0000-0001-5162-9210]
person.identifier.orcidGryko, Daniel T. [0000-0002-2146-1282]
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