The replacement of carbon atoms at the zigzag periphery of a benzo[fg]tetracenyl derivative with an NBN atomic triad allows the formation of heteroatom-doped PAHs isosteres, which expose BN mimics of the amidic NH functions. Their ability to form H-bonded complexes has never been touched so far. Herein we report the first solution recognition studies of peripherally NBN-doped PAHs to form doubly H-bonded DD•AA and ADDA•DAAD-type complexes with suitable complementary H-bonding acceptor partners. The first determination of the Ka in solution showed that the 1:1 association strength is around 27 ± 1 M-1 for the DD•AA complexes in C6D6, whereas it rises to 1820 ± 130 M-1 for the ADDA•DAAD array in CDCl3. Given the interest of BNdoped polyaromatic hydrocarbons in supramolecular and materials chemistry, it is expected that these findings will open new possibilities to design novel materials, where the H-bonding properties of peripheral NH hydrogens could serve as anchors to tailor the organizational properties of PAHs. INTRODUCTION Following the vigorous synthetic developments of polycyclic aromatic hydrocarbons (PAHs), 1 the substitution (i.e., doping) of sp 2-carbon atoms with isoelectronic and isostructural BN couples is re-emerging as a versatile approach to tune the optoelectronic properties of these materials. 2-7 In particular, borazines 8,9 and BN-doped PAHs (e.g., azaborines, 10,11 borazapyrenes, 12,13 borazaphenanthrenes 12,14 borazanaphthalenes, 15,16 borazaanthracene 17,18 and boraazaperylene 19) are now increasingly attracting the attention of the physical and chemical community for their use in a broad spectrum of optoelectronic applications. 20-22 When used to decorate a periphery, nonsubstituted BN couples terminate with NH functions that, being more acidic than the CH analogues, could engage into H-bonding interactions as observed with boronic acids. 23 For instance, Liu and co-workers showed in a seminal report that 1,2-dihydro-1,2-azaborine can act as an H-bonding donor in the solid state and engage into a H-bond with the C=O