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Chemical Reduction of a Nanosized [6]Cyclo-2,7-naphthylene Macrocycle
Zheng Zhou1, Zheng Wei1, Koki Ikemoto2
1Department of Chemistry, University at Albany, State University of New York, 1400 Washington Ave, Albany, NY, 12222, USA.
Abstract:
Chemical reduction of a naphthylene macrocycle, [6]cyclo-2,7-naphthylene ([6]CNAP, 1), with alkali metals, Li and K, revealed the accessibility of the doubly-reduced state of 1. The macrocyclic 12- anion was isolated in different coordination environments and crystallographically characterized. The single-crystal X-ray diffraction confirmed the formation of contact-ion complexes with one Li+ and two K+ ions in THF, and a "naked" dianion in the solvent-separated ion product with K+ ions in the presence of 18-crown-6 ether. The detailed structural analysis of 12- showed that the π-conjugation over the biaryl linkages between naphthylene panels were enhanced upon two-fold reduction, which was rationally explained by theoretical calculations.
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