Black HPHAC: Synthesis and properties of dinitroHPHAC and its reduced global aromaticity in the dication state

Introduction of functional groups on a [Formula: see text]-conjugated system is one of the most promissing methods to modulate their chemical and physical properties. Here, dinitrohexapyrrolohexaazacoronene (dinitroHPHAC) was synthesized, in which two nitro groups are introduced at the same pyrrole ring. The dinitroHPHAC possesses a large dipole moment ([Formula: see text] = 11.7 D at B3LYP/6-31G(d,p)) and showed solvatochromism with decreased HOMO-LUMO energy gap. Interestingly, the colour of the solid is black to the naked eye. The global aromaticity of the dication state is decreased compared with those of pristine HPHAC and mononitroHPHAC.