Überoxidation als Schlüsselschritt im Mechanismus der MoCl<sub>5</sub>‐ vermittelten dehydrierenden Arenkupplung

Schubert, Moritz; Franzmann, P.D.; Leupoldt, Anica Wünsche von; Koszinowski, Konrad; Heinze, Katja; Waldvogel, Siegfried R.

doi:10.1002/ange.201508035

Cited by 14 publications

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“…This leads to a charge injection barrier of only 0.4 eV for a charge transfer from the HOMO of HAT into the LUMO of HATCN. These values compare rather well with energy values derived from optical and electrochemical measurements . The positions of the energy levels highlight the electronic complementarity of HATCN and HAT and their excellent suitability to form CT complexes.…”

Section: Resultssupporting

confidence: 68%

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Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Müller

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et al. 2019

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Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.

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Section: Resultssupporting

confidence: 68%

“…The bandgaps are taken from the UV–vis data, the LUMO of HATCN was derived from the CV curves and the HOMO and LUMO of HAT are taken from ref. .…”

Section: Resultsmentioning

confidence: 99%

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Müller

Schmidt

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et al. 2019

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Efficient Oxidative Coupling of Arenes via Electrochemical Regeneration of 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) under Mild Reaction Conditions

et al. 2017

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The intramolecular dehydrogenative carbon‐carbon bond formation of aromatic rings in the presence of catalytic amounts of an oxidising agent is herein described. The oxidative coupling is realised under indirect anodic conditions, utilising 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as an efficient redox mediator under acidic conditions. In comparison, for the stoichiometric oxidative coupling reaction of hexakis(4‐tert‐butylphenyl)benzene on a 1.0 gram scale, 1.56 g of DDQ were applied, whereas in the present indirect electrochemical version, only 15 mg of DDQ were needed, resulting in significantly easier purifications of the products. The reaction proceeds smoothly using a variety of polyaromatics including terphenyl, quaterphenyl and heptaphenyl derivatives to give polyphenylenes in excellent yields and current efficiencies. A detailed optimisation study, investigations on the electrochemical behaviour of the redox mediator and synthetic applications of the method are discussed.magnified image

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Selektive Synthese teilgeschützter unsymmetrischer Biphenole durch reagens‐ und metallfreie anodische Kreuzkupplung

et al. 2016

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Vorgestellt wird die oxidative Kreuzkupplung von Arenen ohne Abgangsfunktionalitäten oder Katalysatoren. Die selektive Synthese teilgeschützter unsymmetrischer 2,2′‐Biphenole gelang in hohen Ausbeuten an isoliertem Produkt mittels elektroorganischer Synthese. Der Einsatz von elektrischem Strom als Oxidationsmittel ist reagensfrei und verhindert somit die Bildung von Reagensabfällen. Das sichere Verfahren eignet sich für eine einfache ungeteilte Elektrolysezelle sowie für Reaktionen in großem Maßstab. Die Verwendung von O‐Silyl‐geschützten Phenolen resultiert sowohl in gesteigerten Ausbeuten als auch in erhöhten Selektivitäten bei der Synthese der unsymmetrischen 2,2′‐Biphenole. Die Nutzung sperriger Silylgruppen zum Schützen der OH‐Gruppe macht das Produkt weniger anfällig für Folgeoxidationen. Teilgeschützte 2,2′‐Biphenole sind vielseitige Ausgangsverbindungen, die üblicherweise nur aufwändig in geringen Ausbeuten zugänglich sind. Diese Synthesestrategie ermöglicht eine Vielzahl neuer Substratkombinationen für oxidative Kreuzkupplungen.

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Überoxidation als Schlüsselschritt im Mechanismus der MoCl₅‐ vermittelten dehydrierenden Arenkupplung

Cited by 14 publications

References 49 publications

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Efficient Oxidative Coupling of Arenes via Electrochemical Regeneration of 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) under Mild Reaction Conditions

Selektive Synthese teilgeschützter unsymmetrischer Biphenole durch reagens‐ und metallfreie anodische Kreuzkupplung

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Überoxidation als Schlüsselschritt im Mechanismus der MoCl5‐ vermittelten dehydrierenden Arenkupplung

Cited by 14 publications

References 49 publications

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Efficient Oxidative Coupling of Arenes via Electrochemical Regeneration of 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) under Mild Reaction Conditions

Selektive Synthese teilgeschützter unsymmetrischer Biphenole durch reagens‐ und metallfreie anodische Kreuzkupplung

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Überoxidation als Schlüsselschritt im Mechanismus der MoCl₅‐ vermittelten dehydrierenden Arenkupplung