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Clamshell Opening in the Mixed‐Metal Supramolecular Aggregates Formed by Fourfold Reduced Corannulene for Maximizing Intercalated Metal Content
Authors:Dr. Alexander S. Filatov  Dr. Alexander V. Zabula  Dr. Sarah N. Spisak  Prof. Dr. Andrey Yu. Rogachev  Prof. Dr. Marina A. Petrukhina
Affiliation:1. Department of Chemistry, University at Albany, State University of New York, Albany, NY 12222 (USA);2. Department of Chemistry, University of Wisconsin‐Madison (USA);3. Department of Biological and Chemical Sciences, Illinois Institute of Technology (USA)
Abstract:The first members of a new class of supramolecular organometallic compounds with mixed‐alkali‐metal cluster cores, LiK5 and Li3K3, sandwiched between two four‐fold reduced corannulene decks are prepared and fully characterized. The triple‐decker supramolecular anions, [(C20H104?)(LiK5)6+(C20H104?)]2? and [(C20H104?)(Li3K3)6+(C20H104?)]2?, illustrate a record ability of bowl‐shaped and highly charged corannulene to provide all its sites, five benzene rings fused to a central five‐membered ring, for binding of six alkali‐metal ions. The previously unseen engagement of the hub‐site of C20H104? in lithium binding is accompanied by unprecedented shifts up to ?24 ppm in 7Li NMR spectra. The discussion of product formation mechanism, augmented by calculations, is provided.
Keywords:alkali metals  curved carbanions  mixed‐metal systems  reduced corannulenes  X‐ray diffraction
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