Azatriseptanes: Strained Framework Analogs of [7,7,7]Circulenes

The synthesis and characterization of heptagon-embedded polycyclic aromatic compounds are essential for understanding the effect of negative curvature on carbon allotropes such as fullerenes and graphenes that have applications in functional organic materials. However, owing to the synthetic difficulties in functionalizing and embedding seven-membered rings, these strain-challenged structures are relatively unexplored. We report here the synthesis, characterization, and properties of a triarylamine core bridged with ethano chains at the 2,2'-positions. In doing so, we provide access to the first heterocycle containing three fused heptagon rings with a nitrogen at its core (BATA-NHAc). X-ray crystallographic analysis and DFT calculations revealed a remarkably strained structure wherein two of the bridged aryl units approach coplanarity, while the third ring is twisted out of plane at 70°. UV-vis and emission spectroscopies identify red-shifted absorption and concentration-dependent emission profiles, respectively, as a result of the unique conformation and self-assembly properties of BATA-NHAc. Furthermore, cyclic voltammetry shows a decrease in the oxidation potential for BATA-NHAc in comparison to the non-bridged analog. This study opens new avenues in understanding the structure-property relationships of curved π-aromatics and the construction of π-frameworks of increasing complexity.