Information, which can be facilely synthesized via three-step reactions as illustrated in Scheme S1. Firstly, a standard Suzuki coupling reaction condition was adopted to obtain the intermediates. Then, two adjacent C-H bonds were coupled through a Scholl coupling reaction, locking the two plane segments to generate a helical structure. Purified samples were comprehensively characterized using 1 H and 13 C NMR spectroscopy, as well as high-resolution MALDI-TOF-MS. Chiral separation was performed using a CHIRALPAK IA chiral column with varying ratios of methanol and dichloromethane as the mobile phase, resulting in a high enantiomeric excess (>99% ee, as detailed in Figure -32 and Table ). By comparing the experimental circular dichroism spectroscopy and calculated electronic circular dichroism spectroscopy obtained through TD-DFT calculation as shown in Figure and the Supporting Information (SI). DFT calculations revealed that the HOMOs of both emitters are distributed on the nitrogen atoms and carbon atoms at ortho/para positions as electron-donating moieties, while the LUMOs are localized on triaryl boron and carbon atoms at ortho/para positions as electron-acceptor moieties. This distinct distribution of HOMO and LUMO is characteristic of classical BN-MR emitters and contributes to their unique electronic properties. Besides, on both peripheral decoration segments, MR-type orbital distributions were also observed, which should enhance the overall MR property of both emitters, favoring a narrowband emission. A noteworthy observation is that though the similar HOMO distributions of both emitters, the LUMO of BN[8]H-ICz only localized on the parent core without extending to ICz segments, while that of BN[8]H-BO exhibits a nearly uniform distribution across the whole molecular framework. The reason should be attributed to the strong electron-donating property of ICz with only nitrogen atoms while the BO segment shows a bipolar character owing to the coexistence of boron and oxygen atoms. This distinction in LUMO distribution could have implications for the electronic properties of the molecules. We further calculated the charge density difference plots of singlet states, both showing clear short-range charge transfer characters owing to the alternating pattern of the hole and the electron, which further evidenced the MR property of those two emitters.