Molecular Engineering of Chalcogen-Embedded Anthanthrenes via peri-Selective C-H Activation: Fine-Tuning of Crystal Packing for Organic Field-Effect Transistors.

Disclosed herein is a RhCl ₃ -catalyzed peri-selective C-H/C-H oxidative homo-coupling of 1-substituted naphthalenes, which provides a highly efficient and streamlined approach to chalcogen-embedded anthanthrenes from readily available starting materials. Introducing O, S, and Se into the anthanthrene skeleton leads to gradually increased π-π stacking distances but significantly enhanced π-π overlaps with the growth of the hetero-atom radius. Moderate π-π distance, overlap area, and intermolecular S-S interactions endow S-embedded anthanthrene (PTT) with excellent 2D charge-transport properties. Moreover, the transformation of p-type to n-type S-embedded anthanthrenes is realized for the first time via the S-atom oxidation from PTT to PTT-O4. In organic field-effect transistor devices, PTT derivatives exhibit hole transport with mobilities up to 1.1 cm ²  V ^-1  s ^-1 , while PTT-O4 shows electron transport with a mobility of 0.022 cm ²  V ^-1  s ^-1 .
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