Skeletal rearrangement of [4]helicenes under acid conditions; dynamic chirality and improved properties by subsequent peripheral editing

Cationic diaza[4]helicenes are fluorescent scaffolds whose properties can be tuned by late-stage functionalization, although access to unsymmetrically substituted derivatives remains limited. Here, we report an acid-mediated skeletal rearrangement of 1,13-dimethoxyquinacridinium derivatives that enables sequential migration of methoxy groups and provides new 1,11- and 3,11-substituted cationic [4]helicene regioisomers. The rearranged compounds were obtained through reduction or methyl addition, Brønsted acid treatment, and aerobic photooxidation, and their structures supported by spectroscopic and crystallographic analyses. These core-edited dyes display progressive planarization, modified redox behavior, and marked hypsochromic shifts in absorption and emission relative to the parent scaffold. The mono-rearranged platform also undergoes selective peripheral editing by SNAr and demethylation/refunctionalization, giving access to a diverse family of O- and N-substituted derivatives with finely tuned photophysical properties. Importantly, the new helicenes are configurationally labile, with enantiomerization barriers around 19 kcal·mol⁻¹, in contrast to the configurationally stable parent system. This dynamic chirality enables asymmetric induction through covalently bound chiral auxiliaries and ion pairing with enantiopure TRISPHAT, leading to moderate diastereomeric enrichment and measurable ECD responses

Organizational unit: Laboratory of Professor Jérôme Lacour

Type: Dataset

DOI: 10.26037/yareta:dthr7jssmrcndfkvk6bjc7t4ta

License: Creative Commons Attribution 4.0 International

Keywords: cationic diaza[4]helicenes, skeletal rearrangement, acid-mediated, quinacridinium dyes, late-stage functionalization, dynamic chirality, peripheral editing, nucleophilic aromatic substitution, photophysical properties, TRISPHAT

Publication date

01/04/2026

Retention date29/03/2036

Access levelPublic

SensitivityBlue

Contract on the use of data

License

Contributors

Gaucherand, Arthur

Duwald, Romain

Herse, Christelle

Besnard, Céline

Pescitelli, Gennaro

Lacour, Jérôme

Files

5256 Files (1.4 GB)

Quality (0 Reviews)
Usefulness (0 Reviews)

    
      <?xml version="1.0" encoding="UTF-8" standalone="yes"?>
<datacite:resource xmlns:premis="http://www.loc.gov/premis/v3" xmlns:mets="http://www.loc.gov/METS/" xmlns:datacite="http://datacite.org/schema/kernel-4" xmlns:dlcm="http://www.dlcm.ch/dlcm/v3" xmlns:fits="http://hul.harvard.edu/ois/xml/ns/fits/fits_output" xmlns:xlink="http://www.w3.org/1999/xlink">
    <datacite:identifier identifierType="DOI">10.26037/yareta:dthr7jssmrcndfkvk6bjc7t4ta</datacite:identifier>
    <datacite:creators>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Gaucherand, Arthur</datacite:creatorName>
            <datacite:givenName>Arthur</datacite:givenName>
            <datacite:familyName>Gaucherand</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">https://orcid.org/0009-0004-4128-6874</datacite:nameIdentifier>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Duwald, Romain</datacite:creatorName>
            <datacite:givenName>Romain</datacite:givenName>
            <datacite:familyName>Duwald</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">https://orcid.org/0000-0002-9857-1340</datacite:nameIdentifier>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Herse, Christelle</datacite:creatorName>
            <datacite:givenName>Christelle</datacite:givenName>
            <datacite:familyName>Herse</datacite:familyName>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Besnard, Céline</datacite:creatorName>
            <datacite:givenName>Céline</datacite:givenName>
            <datacite:familyName>Besnard</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">https://orcid.org/0000-0001-5699-9675</datacite:nameIdentifier>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Pescitelli, Gennaro</datacite:creatorName>
            <datacite:givenName>Gennaro</datacite:givenName>
            <datacite:familyName>Pescitelli</datacite:familyName>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Lacour, Jérôme</datacite:creatorName>
            <datacite:givenName>Jérôme</datacite:givenName>
            <datacite:familyName>Lacour</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">https://orcid.org/0000-0001-6247-8059</datacite:nameIdentifier>
        </datacite:creator>
    </datacite:creators>
    <datacite:titles>
        <datacite:title>Skeletal rearrangement of [4]helicenes under acid conditions; dynamic chirality and improved properties by subsequent peripheral editing</datacite:title>
    </datacite:titles>
    <datacite:publisher publisherIdentifier="https://ror.org/01swzsf04" publisherIdentifierScheme="ROR" schemeURI="https://ror.org/">Université de Genève, Yareta</datacite:publisher>
    <datacite:publicationYear>2026</datacite:publicationYear>
    <datacite:resourceType resourceTypeGeneral="Dataset">Dataset</datacite:resourceType>
    <datacite:subjects>
        <datacite:subject subjectScheme="keywords" xml:lang="en">cationic diaza[4]helicenes;skeletal rearrangement;acid-mediated;quinacridinium dyes;late-stage functionalization;dynamic chirality;peripheral editing;nucleophilic aromatic substitution;photophysical properties;TRISPHAT</datacite:subject>
    </datacite:subjects>
    <datacite:contributors>
        <datacite:contributor contributorType="ResearchGroup">
            <datacite:contributorName nameType="Organizational">[acac4008-69e9-45cf-ac63-a1752ec63ade] Laboratory of Professor Jérôme Lacour</datacite:contributorName>
            <datacite:affiliation xsi:type="datacite:affiliation" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">[UNIGE-Sciences] Université de Genève - Faculté des Sciences</datacite:affiliation>
            <datacite:affiliation xsi:type="datacite:affiliation" affiliationIdentifier="https://ror.org/01swzsf04" affiliationIdentifierScheme="ROR" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">[UNIGE] Université de Genève</datacite:affiliation>
        </datacite:contributor>
        <datacite:contributor contributorType="ProjectManager">
            <datacite:contributorName nameType="Personal">Lacour, Jérôme</datacite:contributorName>
        </datacite:contributor>
    </datacite:contributors>
    <datacite:dates>
        <datacite:date dateType="Issued">2026-04-01T00:00:00Z</datacite:date>
        <datacite:date dateType="Collected">2026-04-01T00:00:00Z/</datacite:date>
        <datacite:date dateType="Created">2026-04-01T15:24:23.523879Z</datacite:date>
        <datacite:date dateType="Updated">2026-05-13T08:22:33.518159Z</datacite:date>
        <datacite:date dateType="Accepted">2026-05-13T08:22:32.340136151Z</datacite:date>
    </datacite:dates>
    <datacite:alternateIdentifiers>
        <datacite:alternateIdentifier alternateIdentifierType="ARK">ark:64642/rt9dthr7jssmrcndfkvk6bjc7t4ta</datacite:alternateIdentifier>
    </datacite:alternateIdentifiers>
    <datacite:relatedIdentifiers/>
    <datacite:formats>
        <datacite:format>text/plain</datacite:format>
        <datacite:format>inode/x-empty</datacite:format>
        <datacite:format>application/pdf</datacite:format>
        <datacite:format>application/octet-stream</datacite:format>
        <datacite:format>text/xml</datacite:format>
        <datacite:format>audio/mpeg</datacite:format>
        <datacite:format>application/vnd.openxmlformats-officedocument.wordprocessingml.document</datacite:format>
        <datacite:format>application/x-matlab-data</datacite:format>
        <datacite:format>image/png</datacite:format>
        <datacite:format>text/html</datacite:format>
        <datacite:format>application/vnd.openxmlformats-officedocument.spreadsheetml.sheet</datacite:format>
        <datacite:format>application/x-dosexec</datacite:format>
        <datacite:format>application/vnd.ms-excel</datacite:format>
        <datacite:format>application/dec-dx.</datacite:format>
    </datacite:formats>
    <datacite:rightsList>
        <datacite:rights rightsURI="https://www.dlcm.ch/access-level/final">PUBLIC</datacite:rights>
        <datacite:rights rightsURI="https://www.dlcm.ch/data-tag">BLUE</datacite:rights>
        <datacite:rights rightsURI="https://www.dlcm.ch/data-use-policy">LICENSE</datacite:rights>
        <datacite:rights rightsURI="https://creativecommons.org/licenses/by/4.0/" rightsIdentifier="CC-BY-4.0" rightsIdentifierScheme="SPDX">Creative Commons Attribution 4.0 International</datacite:rights>
    </datacite:rightsList>
    <datacite:descriptions>
        <datacite:description descriptionType="Abstract" xml:lang="en">Cationic diaza[4]helicenes are fluorescent scaffolds whose properties can be tuned by late-stage functionalization, although access to unsymmetrically substituted derivatives remains limited. Here, we report an acid-mediated skeletal rearrangement of 1,13-dimethoxyquinacridinium derivatives that enables sequential migration of methoxy groups and provides new 1,11- and 3,11-substituted cationic [4]helicene regioisomers. The rearranged compounds were obtained through reduction or methyl addition, Brønsted acid treatment, and aerobic photooxidation, and their structures supported by spectroscopic and crystallographic analyses. These core-edited dyes display progressive planarization, modified redox behavior, and marked hypsochromic shifts in absorption and emission relative to the parent scaffold. The mono-rearranged platform also undergoes selective peripheral editing by SNAr and demethylation/refunctionalization, giving access to a diverse family of O- and N-substituted derivatives with finely tuned photophysical properties. Importantly, the new helicenes are configurationally labile, with enantiomerization barriers around 19 kcal·mol⁻¹, in contrast to the configurationally stable parent system. This dynamic chirality enables asymmetric induction through covalently bound chiral auxiliaries and ion pairing with enantiopure TRISPHAT, leading to moderate diastereomeric enrichment and measurable ECD responses</datacite:description>
    </datacite:descriptions>
    <datacite:fundingReferences/>
</datacite:resource>