1,2,3,4-Tetrahydro-1,4,5,8-tetraazaanthracene revisited: properties and structural evidence of aromaticity loss

Abstract

The synthesis and properties of 1,2,3,4-tetrahydro-1,4,5,8-tetraazaanthracene (THTAA) – a heterocycle involving both >N–H donating and =N– accepting moieties – have been reinvestigated. Unlike previously reported, THTAA is a thermally stable compound that can be re-sublimed at 300–310 °C without decomposition. Controlled introduction of substituents at the nitrogen atoms of THTAA led to variation of its electron donor/acceptor capability that allowed fine-tuning the absorption properties. The propensity of these compounds and a number of its derivatives to form infinite chains involving >N–H···N= and >N–H···Hal−···N+ atoms is demonstrated by X-ray structure analysis. The DFT level optimized and experimental geometry of THTAA and its derivatives show considerable loss of aromaticity within the quinoxaline moiety.

Keywords

• aromaticity
• density functional calculations
• heterocycles
• hydrogen bonds
• X-ray structures