A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks

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Science  19 Aug 2011:
Vol. 333, Issue 6045, pp. 1008-1011
DOI: 10.1126/science.1208686

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Lithium-coordinated polyaromatic anions such as tetrareduced corannulene, C20H104− (14−), are useful substrates to model and ultimately improve the graphitic electrodes in lithium-ion (Li+) batteries. Previous studies suggested that 14− forms dimers encasing four Li+ ions in solution. Here, we report a single-crystal x-ray diffraction analysis confirming the formation of a sandwich-type supramolecular aggregate with a high degree of alkali metal intercalation. In contrast to the prior model, our data reveal that five Li+ ions are sandwiched between the two tetrareduced corannulene decks, and 7Li nuclear magnetic resonance spectroscopy delineates a conserved structure in tetrahydrofuran solution. Remarkably, the sandwich is robust in both solution and solid states even in the presence of crown ethers that compete for Li+ coordination. These results should help elucidate Li+ intercalation motifs between curved carbon surfaces more broadly.

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