Peri‐Functionalized Tetraazaperylenes: Strong Emitters for Molecular Polaritonics

Abstract

The functionalization of the peri position of the bay chlorinated tetraazaperylene was investigated by varying the donor behavior of the substituents to assess the resulting photophysical and electrochemical properties. To accomplish this, electron donating alkyl‐ and arylsulfido substituents, methoxy and methyl groups were selectively introduced into the peri position via a nucleophilic aromatic substitution of the perchlorinated tetraazaperylene. Both the alkylated and benzylated thioethers displayed high fluorescence quantum yields of up to 80 %. Compounds from the latter group were integrated in resonant optical microcavities to achieve strong light‐matter coupling. The formation of exciton‐polaritons was observed by angle‐dependent reflectivity and photoluminescence that could be tuned by variation of the concentration of the fluorophores and of the thickness of the cavity.

Two-photon microprinting of 3D emissive structures using tetraazaperylene-derived fluorophores

“…The octachlorinated tetraazaperylene 1 has proved to be a synthetically useful starting compound in our investigation of tetraazaperylene chemistry, giving access to octaazapero-pyrenes (OAPP) 27 and OAPPDO 26 dyes as well as other peri functionalized tetraazaperylene derivatives. 28 Two different N -benzyl substituents were chosen to vary the solubility, solid state packing as well as the compatibility and incorporation of OAPPDOs in a photoresist for microprinting. OAPPDOs 3a and 3b were synthesized via the reaction sequence depicted in Scheme 1.…”

Tetraazacoronenes and Their Dimers, Trimers and Tetramers

“…Recently, we have begun to apply isosteric [CH→N] substitution to perylene chemistry giving synthetic access to various types of peri ‐functionalized tetraazaperylene derivatives [9–11] . Herein we report two different strategies to laterally expand the azaperylene core in its bay ‐positions to give access to the corresponding tetraazacoronenes.…”

Tetraazacoronene und ihre Dimere, Trimere und Tetramere

“…In jüngster Zeit haben wir begonnen, die isosterische [CH→N] Substitution auf die Perylenchemie anzuwenden, wodurch verschiedene Typen peri ‐funktionalisierter Tetraazaperylenderivate zugänglich gemacht wurden [9–11] . Hier berichten wir über zwei verschiedene Synthesestrategien, um den Azaperylenkern in bay ‐Position zu anellieren, was zu den entsprechenden Tetraazacoronenen führt.…”

“…[8b] In jüngster Zeit haben wir begonnen, die isosterische [CH!N] Substitution auf die Perylenchemie anzuwenden, wodurch verschiedene Typen peri-funktionalisierter Tetraazaperylenderivate zugänglich gemacht wurden. [9][10][11] Hier berichten wir über zwei verschiedene Synthesestrategien, um den Azaperylenkern in bay-Position zu anellieren, was zu den entsprechenden Tetraazacoronenen führt. Dichtefunktionaltheoretische (DFT) Modellierung auf B3LYP/ Def2-TZVPP-GD3(BJ) [12][13][14][15][16][17] Niveau zeigte, dass die Aza-Substitution die HOMO-und LUMO-Energien um etwa 1 eV verringern (siehe Abbildung 1).…”