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Disclosed herein is a RhCl3‐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 cm2 V−1 s−1, while PTT‐O4 shows electron transport with a mobility of 0.022 cm2 V−1 s−1. [ABSTRACT FROM AUTHOR]

An unprecedented Rh-catalyzed ketone-directed vinylic C−H activation/[4+2] O-annulation of α-aryl enones with internal alkynes followed by a Cu-catalyzed ring contraction in air to provide multiaryl-substituted furan derivatives has been developed. The preliminary mechanism study identifies the active pyrylium salt as the key intermediate. [ABSTRACT FROM AUTHOR]

Little is known about the formation pathway of colloidal semiconductor magic‐size clusters (MSCs). Here, the synthesis of the first single‐ensemble ZnSe MSCs, which exhibit a sharp optical absorption singlet peaking at 299 nm, is reported; their formation is independent of Zn and Se precursors used. It is proposed that the formation of MSCs starts with precursor self‐assembly followed by Zn and Se covalent bond formation to result in immediate precursors (IPs) which can transform into the MSCs. It is demonstrated that the IPs in cyclohexane appear transparent in optical absorption, and become visible as MSCs exhibiting one sharp optical absorption peak when a primary amine is added at room temperature. It is shown that when the preparation of the IP is controlled to be within the induction period, which occurs prior to nucleation and growth of conventional quantum dots (QDs), the resulting MSCs can be produced without the complication of the simultaneous coproduction of conventional QDs. The present study reveals the existence of precursor self‐assembly which leads to the formation of colloidal semiconductor MSCs and provides insights into a multistep nucleation process in cluster science. Precursor self‐assembly, with ZnSe as a model system is proposed as a general pathway for the formation of colloidal semiconductor magic‐size clusters (MSCs). The self‐assembly followed by ZnSe bond formation gives rise to the formation of immediate precursors of MSCs prior to formation of conventional quantum dots. ZnSe MSC‐299 forms from reactions of various Zn and Se precursors. [ABSTRACT FROM AUTHOR]