Publikation:

Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors

Lade...
Vorschaubild

Dateien

Casper_2-8a1xxs965uap6.pdf
Casper_2-8a1xxs965uap6.pdfGröße: 5.57 MBDownloads: 177

Datum

2021

Herausgeber:innen

Kontakt

ISSN der Zeitschrift

Electronic ISSN

ISBN

Bibliografische Daten

Verlag

Schriftenreihe

Auflagebezeichnung

ArXiv-ID

Internationale Patentnummer

Angaben zur Forschungsförderung

Projekt

Open Access-Veröffentlichung
Open Access Hybrid
Core Facility der Universität Konstanz

Gesperrt bis

Titel in einer weiteren Sprache

Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published

Erschienen in

Chemistry – A European Journal. Wiley. 2021, 27(42), pp. 10854-10868. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.202101032

Zusammenfassung

Three new electrochromic ferrocenyl triarylmethylium dyes with fluorenylium ( 1a + , 1b + ) or thioxanthylium ( 1c + ) residues were selected in order to keep the intrinsic differences of redox potentials for ferrocene oxidation and triarylmethylium reduction small and to trigger valence tautomerism. UV/Vis/NIR and quantitative EPR spectroscopy identified paramagnetic diradical isomers 1a +•• ‐1c +•• alongside diamagnetic forms 1a + ‐1c + , which renders these complexes magnetochemical switches. The diradical forms 1a +•• ‐1c +•• as well as the one‐electron reduced triarylmethyl forms of the complexes were found to dimerize in fluid solution. For radical 1a • , dimerization occurs on the timescale of cyclic voltammetry, which allowed us to determine the kinetics and equilibrium constant for this process by digital simulation. Mößbauer spectroscopy indicated that 1a + and 1b + retain VT even in the solid state. UV/Vis/NIR spectroelectrochemistry revealed the polyelectrochromic behaviour of these complexes by establishing distinctly different electronic absorption profiles of the corresponding oxidized and reduced form s.

Zusammenfassung in einer weiteren Sprache

Fachgebiet (DDC)
540 Chemie

Schlagwörter

Valence Tautomerism, Magnetochemical Switches, Tritylium Dyes, Ferrocene, Mößbauer Spectroscopy

Konferenz

Rezension
undefined / . - undefined, undefined

Forschungsvorhaben

Organisationseinheiten

Zeitschriftenheft

Zugehörige Datensätze in KOPS

Zitieren

ISO 690WINTER, Rainer F., Larissa A. CASPER, Michael LINSEIS, Serhiy DEMESHKO, Mykhailo AZARKH, Malte DRESCHER, 2021. Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors. In: Chemistry – A European Journal. Wiley. 2021, 27(42), pp. 10854-10868. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.202101032
BibTex
@article{Winter2021-07-26Tailo-53491,
  year={2021},
  doi={10.1002/chem.202101032},
  title={Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors},
  number={42},
  volume={27},
  issn={0947-6539},
  journal={Chemistry – A European Journal},
  pages={10854--10868},
  author={Winter, Rainer F. and Casper, Larissa A. and Linseis, Michael and Demeshko, Serhiy and Azarkh, Mykhailo and Drescher, Malte}
}
RDF
<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/53491">
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/53491/1/Casper_2-8a1xxs965uap6.pdf"/>
    <dc:creator>Winter, Rainer F.</dc:creator>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:creator>Azarkh, Mykhailo</dc:creator>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:creator>Drescher, Malte</dc:creator>
    <dcterms:title>Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors</dcterms:title>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/53491/1/Casper_2-8a1xxs965uap6.pdf"/>
    <dc:contributor>Azarkh, Mykhailo</dc:contributor>
    <dc:creator>Casper, Larissa A.</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-04-27T06:53:24Z</dcterms:available>
    <dcterms:issued>2021-07-26</dcterms:issued>
    <dc:language>eng</dc:language>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-04-27T06:53:24Z</dc:date>
    <dc:rights>terms-of-use</dc:rights>
    <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/53491"/>
    <dc:contributor>Casper, Larissa A.</dc:contributor>
    <dc:contributor>Demeshko, Serhiy</dc:contributor>
    <dc:creator>Demeshko, Serhiy</dc:creator>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:abstract xml:lang="eng">Three new electrochromic ferrocenyl triarylmethylium dyes with fluorenylium ( 1a + , 1b + ) or thioxanthylium ( 1c + ) residues were selected in order to keep the intrinsic differences of redox potentials for ferrocene oxidation and triarylmethylium reduction small and to trigger valence tautomerism. UV/Vis/NIR and quantitative EPR spectroscopy identified paramagnetic diradical isomers 1a +•• ‐1c +•• alongside diamagnetic forms 1a + ‐1c + , which renders these complexes magnetochemical switches. The diradical forms 1a +•• ‐1c +•• as well as the one‐electron reduced triarylmethyl forms of the complexes were found to dimerize in fluid solution. For radical 1a • , dimerization occurs on the timescale of cyclic voltammetry, which allowed us to determine the kinetics and equilibrium constant for this process by digital simulation. Mößbauer spectroscopy indicated that 1a + and 1b + retain VT even in the solid state. UV/Vis/NIR spectroelectrochemistry revealed the polyelectrochromic behaviour of these complexes by establishing distinctly different electronic absorption profiles of the corresponding oxidized and reduced form s.</dcterms:abstract>
    <dc:contributor>Drescher, Malte</dc:contributor>
    <dc:contributor>Linseis, Michael</dc:contributor>
    <dc:creator>Linseis, Michael</dc:creator>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Winter, Rainer F.</dc:contributor>
  </rdf:Description>
</rdf:RDF>

Interner Vermerk

xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter

Kontakt
URL der Originalveröffentl.

Prüfdatum der URL

Prüfungsdatum der Dissertation

Finanzierungsart

Kommentar zur Publikation

Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Ja
Begutachtet
Ja
Diese Publikation teilen