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An oxidative ring‐closure reaction of a tetranaphthylpyrene derivative led to the synthesis of a 56 all‐carbon conjugated tetrabenzoperipentacene. In the single‐crystal X‐ray structure, three molecules make a triple‐layered cluster by π‐stacking, wherein each layer rotates by 120°, and is thus considered a petit β‐graphite. As for the optical properties, the Stokes shift is extremely small (10 cm−1...
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