Based on retrosynthetic analysis, the skeleton of Clar's goblet can be viewed as the fusion of two olympicenyl radicals , with two new C-C bonds formed in the disjoint region. Therefore, a straightforward synthetic strategy is to create these two connecting bonds between olympicenyl radicals or derivatives through intermolecular radical-radical coupling, which was also the idea behind Clar's attempt 1 . However, olympicenyl radicals or derivatives have zero spin density on these two bottom carbons, leading to the failure of radical-radical coupling. We thus designed a modified diradical precursor, making this strategy feasible (Fig. ). Dihydroxyl naphthanthrone (1) was the starting compound, which was further transformed into diradical precursor 2 under the oxidative condition developed by Zeng's group . The diradical precursor 2 has considerable spin density on the desired carbons, as suggested by its carbon-centered radical resonance structure. Intermolecular radical-radical coupling between two molecules of 2 and subsequent simultaneous dehydrogenation driven by aromaticity, led to the formation of the proposed intermediate 3. This dimerized intermediate 3 was further reduced into tetrahydroxyl 4 using Na2S2O4. Due to their poor solubilities, intermediates 3 and 4 were directly used in the next steps without characterization. The hydroxyl groups in 4 were converted to n-butoxy ( n BuO) groups in 5 by reacting with excess K2CO3 and 1bromobutane. The key precursor 5 with the target carbon skeleton can be fully characterized including single-crystal X-ray diffraction analysis (Supplementary Fig. ). In the final step, treatment of diketone 5 with excess lithium (triisopropylsilyl)acetylide followed by reductive dehydroxylation with H2SnCl4 resulted in the formation of target Clar's goblet -cg-1. However, the high reactivity of cg-1, with an estimated half-life time (τ1/2) of 8 hours (Supplementary Fig. ), limits further reliable characterization. We thus revised the molecular design of Clar's goblet to cg-2 by introducing bulky aryl substituents at the periphery to increase its kinetical inertness. Ir-catalyzed borylation reaction of compound 5 produced compound 6 with four pinacol boronate (Bpin) groups. Subsequent Suzuki coupling reaction allowed us to install aryl substituents at the peripheral positions, yielding the diketone precursor 7. This precursor underwent the same nucleophilic addition/reductive dehydroxylation steps to generate cg-2. The sterically hindered substituents successfully made cg-2 more inert, with a substantially extended τ1/2 of 6 days (Supplementary Fig. ), allowing for in-depth investigation. Single crystals of cg-2 were obtained by slow vapor diffusion of acetonitrile into its chlorobenzene solution in a glovebox filled with nitrogen gas. Crystallographic analysis unambiguously demonstrated the structure. The skeleton of Clar's goblet is surrounded by peripheral bulky substituents, with a head-to-tail distance of 11.3 Å (Fig. ). The presence of middle n BuO chains induces a twist in the backbone with an angle of about 37 o . Moreover, this twisted backbone imparts intrinsic chirality to cg-2, resulting in Pand Menantiomers. The packing structure shows the racemic composition (Fig. ). Interestingly, two identical enantiomers form a pseudo-molecular box, encapsulating two chlorobenzene molecules inside. The formation of this super-structure is driven by hydrogen bonding, π•••π interactions, and CH•••π interactions (Supplementary Fig. ). The distance between the top and bottom cg-2 in the super-structure is approximately 6.8 Å, indicating weak intermolecular spin-spin interactions.