The replacement of CC for isoelectronic BN units generates superficially similar molecules, but the BN congeners often have distinct properties. Due to this phenomenon BN incorporation into organic materials has received significant attention, with it now an established approach to modify physical and optoelectronic properties. This approach has been applied to helicenes, with BN incorporation within the helical backbone of [4]helicenes (e.g. A and B, Fig. ) found to improve the fluorescence efficiency relative to the all carbon [4]helicene. However, the incorporation of BN units into the helical backbone of the higher [n]helicenes (n ≥ [5], necessary for configurational stability) is underdeveloped, with no simple BN analogues of the higher helicenes, [5]-and [6]helicene (C and D), reported to date to our knowledge (all examples published to date are π extended BN-helicenes, e.g. E). While four coordinate at boron BN units and other boron units have been incorporated into the backbone of higher helicenes, these do not contain helical cores isoelectronic to helicenes C and D.