Synthesis, aromatization and cavitates of an oxanorbornene-fused dibenzo[de,qr]tetracene nanobox

Abstract

Oxanorbornene-fused double-stranded macrocycles, represented by kohnkene, are not only synthetic precursors toward short segments of zigzag carbon nanotubes but also typical cavitands processing an intrinsic cavity. However, their capability to bind guest molecules in solution remained unexplored. Herein we report a new member of oxanorbornene-fused double-stranded macrocycles, which is named a nanobox herein because of its shape. Reductive aromatization of this oxanorbornene-fused nanobox leads to observation of a new zigzag carbon nanobelt by high resolution mass spectroscopy. The fluorescence titration and NMR experiments indicate that this nanobox encapsulates C₇₀ in solution with a binding constant of (3.2 ± 0.1) × 10⁶ M⁻¹ in toluene and a high selectivity against C₆₀ and its derivatives. As found from the X-ray crystallographic analysis, this nanobox changes the shape of its cross-section from a rhombus to nearly a square upon accommodating C₆₀.