In summary, we have investigated the oxidative cleavage of the inner double bonds in dibenzo[g,p]chrysene (DBC; 1a) and we have developed four interesting strands of research in this context. Firstly, we have shown that it is possible to scale this reaction up to yield 23 g of eightphenone (2a) in one reaction. Secondly, we synthesized four brominated derivatives of 2a from brominated DBC precursors. It was then possible, using Suzuki-Miyaura cross-coupling reactions of these building blocks, to readily obtain p-tolyl-derivatives that exhibit circularly polarized luminescence with high gCPL values of more than 1 × 10 -2 . Thirdly, we investigated the fundamental properties of 2a, which revealed that (1) during crystallization, 2a undergoes spontaneous resolution to afford a conglomerate; (2) 2a is configurationally stable with an inversion barrier of 30 kcal mol -1 ; (3) the photoexcitation of 2a creates a triplet state that emits circularly polarized phosphorescence with a high g value of 3.3 × 10 -2 ; and (4) the carbonyl groups of 2a can undergo conventional organic transformations, such as a hydride reduction, nucleophilic alkynylation, and Wittig reactions. Finally, we synthesized three nonplanar π systems that consist of two figure-eight subunits. These highly distorted structures can be expected to be difficult to construct using conventional bottom-up approaches, and, to the best of our knowledge, represent the first examples of nonplanar π-systems that consist of more than two figure-eight subunits. The present results demonstrate a new synthetic strategy that we have coined 'constructive destruction'. Constructive destruction should be thought of as an internalmodification strategy of conjugated π-systems and is a powerful strategy to create challenging molecular fragments. This approach can be expected to become helpful in the design and development of future materials.