Synthesis and Optical Properties of Diaza‐ and Tetraazatetracenes

Abstract

A series of functionalized diaza- and tetraazatetracenes was synthesized, either by condensation of an aromatic diamine with an ortho-quinone/diethyloxalate followed by chlorination with POCl(3) to give diazatetracenes or by palladium-catalyzed coupling of a phenylenediamine with various 2,3-dichloroquinoxalines to give tetraazatetracenes (after oxidation with MnO(2)). Representative examples included halogenated and nitrated derivatives. The optical properties of these azatetracenes were discussed with respect to their molecular structures and substitution patterns. The diazatetracenes and tetraazatetracenes formed two different groups that had significantly different electronic structures and properties. Furthermore, 1,2,3,4-tetrafluoro-6,11-bis((triisopropylsilyl)ethynyl)benzo[b]phenazine was synthesized, which is the first reported fluorinated diazatetracene. Single-crystal X-ray analysis of this compound is reported.

Synthesis, Physical Properties, and Anion Recognition of Two Novel Larger Azaacenes: Benzannelated Hexazaheptacene and Benzannelated N,N′‐Dihydrohexazaheptacene

“…f, 8c, 9 Recently, Bunz et al. found that N‐heteroacenes are resistive to degradation (oxidation or dimerization) as compared to their parent oligoacenes 6a. b, d More importantly, it has been shown that the number, position, and valence states of N atoms in frameworks contribute significantly to the physical properties of N‐substituted PAHs.…”

Soluble Diazaiptycenes: Materials for Solution-Processed Organic Electronics

“…This trend is observed in solutions, where 2a exhibits a deep colour in daylight and strong yellow-orange emission under illumination at 365 nm, while 1a and 3a are less strongly fluorescent ( Figure 1). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Figure 2 shows the absorption spectra of compounds 1a-3a, compared with those of the Nheteroacenes 1b-3b 14,17,18 in hexane. The diazaiptycenes showed similar curves compared to the diazaacenes, indicating that there is no significant electronic coupling between the two isolated benzene rings and the azaacene-unit.…”

Imide‐Fused Diazatetracenes: Synthesis, Characterization, and Application in Perovskite Solar Cells

“…It is essential to lower the LUMO energy level of azatetracenes to achieve better n‐type performance. From the synthetic perspective, the introduction of electron‐withdrawing units could evidently deepen the LUMO of azatetracenes . Mark et al.…”