The functionalization of the peripheral sites of the benzene rings of 2a is shown in Figure . Bromination of 2a with N-bromosuccinimide (NBS) furnished 2,7,10,15tetrabromoeightphenone (2e) in 15% yield. The low yield is due to the formation of byproducts with three or five bromo groups. In contrast, iodination with N-iodosuccinimide (NIS) proceeded selectively, affording 2e in 58% yield. Brominated eightphenones 2c and 2e were subsequently used in Suzuki-Miyaura cross-coupling reactions with 4-methylphenylboronic acid, and furnished the corresponding p-tolylated derivatives 6 and 7 in 75% and 82% yield, respectively. A single-crystal X-ray diffraction analysis of 7 revealed a π-extended figure-eight structure (Figure ). 2,7,10,15-Tetra(p-tolyl)eightphenone ( ) exhibited fluorescence at 482 nm in CH2Cl2 with a quantum yield of 2.7% and a lifetime of 6.4 ns (Figure ). The enantiomers of 7 were separated using HPLC (Figure ). The CD and CPL spectra of the obtained fractions are shown in Figure , whilst the absolute configuration of the enantiomer has been determined by the transformation of the corresponding enantiomerically pure brominated precursor whose configuration has been confirmed by X-ray diffraction analysis (Figures ). Importantly, these enantiomers display intense CPL with a high |gCPL| value of 1.4 × 10 -2 . 3,6,11,14-Tetra(ptolyl)eightphenone (6) also showed CPL with a |gCPL| value of ca. 1 × 10 -2 (Figure ). These g values are high and compare favorably with previously reported organic CPL emitters. TD-DFT calculations on 6 and 7 revealed that their electric and magnetic transition dipole moments adopt parallel arrangements due to their D2-symmetric structures, which is ideal for archiving high gCPL values. To create more challenging structures that consist of two figure-eight subunits, we subjected three nanographene molecules, tetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene (8), tetrabenzo[a,c,f,k]phenanthro[9,10-m]tetraphene (9), and hexabenzo[a,c,fg,j,l,op]tetracene (10), to constructive destruction (Figure ). Treatment of 8-10 with Na2Cr2O7•2H2O in refluxing propionic acid cleaved the two inner double bonds of these molecules to furnish 11, 12, and 13 in 50%, 38%, and 16% yield, respectively. The oxidatively cleaved C-C bonds are identical to the local double bonds predicted by Clar's rule. This empirical assumption was corroborated using the harmonic oscillator model of aromaticity (HOMA) values (Figure ). These results offer rational guidelines for predicting the selectivity of the oxidative cleavage of the inner double bonds in such nanographene molecules. X-ray diffraction analyses of 11, 12, and 13 revealed that they possess remarkably distorted structures and that their local eightphenone subunits adopt figure-eight conformations (Figure ). In the structures of 11 and 12, two eightphenone subunits share one benzene ring, which results in the formation of S-shaped structures. Compound 11 is achiral because the two eightphenone subunits are mirror images of each other, creating a rotatory reflection axis orthogonal to the central benzene ring. Conversely, 12 is chiral because the two eightphenone subunits adopt the same configuration. In the case of 13, two eightphenone subunits with the same configuration share a biphenyl unit, which affords a helical structure in which three biphenyl segments are linked by carbonyl groups. The twisting angle between the two phenylphenyl linkages at both ends is very large (270°) despite its short distance (6.2 Å), thus creating a short pitch (8.3 Å). To the best of our knowledge, 11-13 are the first examples of nonplanar π-systems that consist of more than two figure-eight subunits. These highly distorted structures can be expected to be difficult to construct using conventional bottom-up approaches.