Silas C Eiden, Erik Misselwitz, Frank Rominger, Milan Kivala
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引用次数: 0
Abstract
We report a series of cyclopentannulated decacyclenes that act as remarkable multistage electron acceptors. The compounds were synthesized in a modular approach via Yamamoto cyclotrimerization of brominated pyracylene precursors, allowing the introduction of electron-withdrawing, -donating, and solubilizing fluoro, methoxy, and tert-butyl moieties, respectively. The subsequent π-expansion of the polycyclic scaffold was achieved by oxidative cyclodehydrogenation. X-ray crystallographic analysis revealed the propeller-shaped geometry of the decacyclene core with a pronounced bond length alternation in the central six-membered ring and the columnar packing motif in the solid state. Depending on the substitution pattern, the compounds are capable of up to six reversible reductions within a particularly narrow potential range between -1.45 and -2.86 V under electrochemical conditions. This result is in stark contrast to only two reductions of parent decacyclene and clearly demonstrates the major impact of strategic cyclopentannulation on the redox properties of the sp2-carbon scaffold, which was further supported by density functional theory studies.
期刊介绍:
Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics.
Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews.
A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal.
Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).