DiazaChrysenes (DC): Nitrogen-Containing π-Extended Molecules for Photocatalytic C–H Amination

We report a new class of nitrogen-containing π-extended heterocycles, DiazaChrysenes (<b>DC</b>s), and their dimeric analogues (<b>dDC</b>s) as metal-free photocatalysts for C-H amination. <b>DC</b>s featuring a quinolino[1,2-<i>c</i>]quinazolin-5-ium core were synthesized via electrophilic amide activation and arylation. The resulting compounds displayed tunable photophysical and redox properties, with CF₃-substituted <b>DC</b>s enabling the C-H amination of arenes with azoles under visible light and aerobic conditions, achieving yields up to 85%. The reaction tolerated a range of arene and azole substrates without requiring metal salts or additives. In contrast, <b>dDC</b>s exhibited diminished activity, likely due to their extended π-curvature. Computational studies, including NCI, ACID, and NICS analyses, revealed locally aromatic but electronically isolated π-systems and deshielded central 8-membered cores. This work highlights the utility of <b>DC</b> scaffolds as synthetically accessible and redox-tunable organic photocatalysts.