Multiple Helicenes Defected by Heteroatoms and Heptagons with Narrow Emissions and Superior Photoluminescence Quantum Yields**

The incorporation of heteroatoms and/or heptagons as the defects into helicenes expands the variety of chiroptical materials with novel properties. However, it is still challenging to construct novel boron-doped heptagon-containing helicenes with high photoluminescence quantum yields (PLQYs) and narrow full-width-at-half-maximum (FWHM) values. We report an efficient and scalable synthesis of a quadruple helicene 4Cz-NBN with two nitrogen-boron-nitrogen (NBN) units and a double helicene 4Cz-NBN-P1 bearing two NBN-doped heptagons, the latter could be formed via a two-fold Scholl reaction of the former. The helicenes 4Cz-NBN and 4Cz-NBN-P1 exhibit excellent PLQYs up to 99 % and 65 % with narrow FWHM of 24 nm and 22 nm, respectively. The emission wavelengths are tunable via stepwise titration experiments of 4Cz-NBN-P1 toward fluoride, enabling distinguished circularly polarized luminescence (CPL) from green, orange (4Cz-NBN-P1-F1) to yellow (trans/cis-4Cz-NBN-P1-F2) with near-unity PLQYs and broader circular dichroism (CD) ranges. The five structures of the aforementioned four helicenes were confirmed by single crystal X-ray diffraction analysis. This work provides a novel design strategy for construction of non-benzenoid multiple helicenes exhibiting narrow emissions with superior PLQYs.