A Four-Step Synthesis of Substituted 5,11-Dicyano-6,12-diaryltetracenes with Enhanced Stability and High Fluorescence Emission

作者：Kerisit Nicolas; Gawel Przemyslaw; Levandowski Brian; Yang Yun Fang; Garcia Lopez Victor; Trapp Nils; Ruhlmann Laurent; Boudon Corinne; Houk Kendall N; Diederich Francois

来源：Chemistry - A European Journal, 2018, 24(1): 159-168.

DOI：10.1002/chem.201703903

• decyanation
• photostability
• polycyclic aromatic hydrocarbons
• tetraaryl[3]cumulenes
• tetracenes

A four-step synthesis of substituted 5,11-dicyano-6,12-diaryltetracenes was developed, starting from readily available para-substituted benzophenones. The key step of this straightforward route is the complex cascade reaction between tetraaryl[3]cumulenes and tetracyanoethene (TCNE) resulting in 5,5,11,11-tetracyano-5,11-dihydrotetracenes. The mechanism of this transformation was reinvestigated by means of theoretical calculations. The target tetracenes were obtained by a newly developed decyanation/aromatization reaction catalyzed by Cu-I or Cu-II complexes in solution, conditions compatible with a broad range of functional groups. A computational mechanistic study sheds light on this transformation. Structures of all tetracene derivatives were confirmed by X-ray crystallography. The presented dicyanotetracene derivatives exhibit outstanding optoelectronic properties and enhanced photostability, significantly surpassing the reference rubrene (5,6,11,12-tetraphenyltetracene).

• 出版日期2018-1-2