Synthesis of Cyano-Substituted Diaryltetracenes from Tetraaryl[3] cumulenes**

Date

2014-04-22

Author

GAWEL, Przemyslaw
Dengiz, Çağatay
FINKE, Aaron D.
TRAPP, Nils
BOUDON, Corinne
GISSELBRECHT, Jean-Paul
DIEDERICH, Francois

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A versatile, two-step synthesis of highly substituted, cyano-functionalized diaryltetracenes has been developed, starting from easily accessible tetraaryl[3]cumulenes. This unprecedented transformation is initiated by [2+2] cycloaddition of tetracyanoethylene (TCNE) to the proacetylenic central double bond of the cumulenes to give an intermediate zwitterion, which after an electrocyclization cascade and dehydrogenation yields 5,5,11,11-tetracyano-5,11-dihydrotetracenes in a one-pot procedure. A subsequent copper-assisted decyanation/aromatization provided the target 5,11-dicyano-6,12-diaryltetracene derivatives. All of the postulated structures were confirmed by X-ray crystallography. The new chromophores are thermally highly stable and feature promising fluorescence properties for potential use in optoelectronic devices. They are selective chemosensors for Cu-I ions, which coordinate to one of the CN substituents and form a 1:1 complex with an association constant of K-a=1.5x10(5)Lmol(-1) at 298K.

Subject Keywords

Tetracenes, Electrocyclization, Chemosensors, [3]cumulenes, [2+2] cycloaddition

URI

https://hdl.handle.net/11511/40951

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

DOI

https://doi.org/10.1002/anie.201402299

Collections

Department of Chemistry, Article

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Citation Formats

P. GAWEL et al., “Synthesis of Cyano-Substituted Diaryltetracenes from Tetraaryl[3] cumulenes**,” ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, pp. 4341–4345, 2014, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/40951.