AzaBPDIs with aromatic side groups presenting a hydroxy group oriented toward the ortho position of the AzaBPDI should be efficiently cyclized into an oxygen-incorporating 6-member rings by coppercatalyzed oxidative C-H activation. AzaBPDI 1a, 1b, 3, and BACD 5 and 7 were prepared via our recently reported 20 light-mediated azabenzannulation of PDIs methodology in good yields (see SI Scheme S1, S2, S3, S4 and S5). The annulation reaction afforded compounds 2a and 2b in a moderate 47% and a good 65% yields, respectively. The difference between the yields are attributed to the improved solubility of the 2-octyldodecyl peripheral chains compared to the pentyl ones. O-annulated AzaBPDI 4 featuring an extended π system was obtained in 55% yield despite its poor solubility. BACD 5 was efficiently converted into a large double ortho O-annulated O-BACD 6. The same reaction performed on BACD 7 afforded only traces of the target materials, along with unidentified decomposition products. A non-symmetrical O-annulated BACD dimer with a central phenyl ring was prepared. The sequence involved a double visible-light azabenzannulation between regiopure planar and the three added aromatic rings are parallel to the former PDI core (Figure ). The molecules crystallize as dimers separated by a distance of 3.3 Å (Figure ) demonstrating a tight π-stacking originating from strong donor-acceptor interactions, as the electron-rich side-groups of one molecule are interacting with the electron-deficient diimide core of the second one (Figure ). Furthermore, the The optoelectronic properties (Table ) of the O-doped nanographenes were investigated by a combination of absorption/emission spectroscopy and cyclic voltammetry (CV). After annulation, the absorption profile of all compounds are shifted toward longer wavelengths (see Figures 3, S1, S9, S17