Tetrazo[1,2‐ <i>b</i> ]indazoles: Straightforward Access to Nitrogen‐Rich Polyaromatics from <i>s</i> ‐Tetrazines

The straightforward access to a new class of aza-polyaromatics is reported. Starting from readily available fluorinated s-tetrazine, cyclization process with azide leads the formation an unprecedented tetrazo[1,2-b]indazole or bis-tetrazo[1,2-b]indazole (cis and trans conformers). Based on nitrogen core, further N-directed palladium-catalyzed ortho-C−H bond functionalization allows introduction halides acetates. physicochemical properties these compounds were studied by joint experimental/theoretical approach. tetrazo[1,2-b]indazoles display solid-state π-stacking, low reduction potential, absorption in visible range up near-infrared, intense fluorescence, depending molecular structure.