Boron-Cluster Embedded Necklace-Shaped Nanohoops

The combination of carbon-based nanohoops with other functional organic molecular structures should lead to the design of new molecular configurations with interesting properties. Here, necklace-like nanohoops embedded with carborane were synthesized for the first time. The unique deboronization of o-carborane has led to the facile preparation of ionic nanohoop compounds. Nanohoops functionalized by nido-o-carborane show excellent fluorescence emission, with a solution quantum yield of up to 90.0 % in THF and a solid-state quantum efficiency of 87.3 %, which opens an avenue for the applications of the nanohoops in OLEDs and bioimaging.     

Heptagon-Containing Nanographene Embedded into [10]Cycloparaphenylene

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C₆₀ and C₇₀, with remarkably large binding constants (ca. 10⁷ M⁻¹), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These results demonstrate saddle-shaped PAHs with dibenzocycloheptatrienone motifs as structural components for new macrocycles displaying molecular receptor abilities and versatile photochemical responses with promising electron-donor properties in host-guest complexes.     

A Fourfold Gold(I)−Aryl Macrocycle with Hyperbolic Geometry and its Reductive Elimination to a Carbon Nanoring Host

An ethylene glycol-decorated [6]cyclo-meta-phenylene (CMP) macrocycle was synthesized and utilized as a subunit to construct a fourfold Au^I₂−aryl metallacycle with an overall square arrangement. The corners consist of rigid dinuclear gold(I) complexes previously known to form only triangular metallacycles. The interplay between the conformational flexibility of the [6]CMP macrocycle and the rigid dinuclear gold(I) moieties enable the square geometry, as revealed by single-crystal X-ray diffraction. The formation of the gold complex shows size-selectivity compared to an alternative route using platinum(II) corner motifs. Upon reductive elimination, an all-organic ether-decorated carbon nanoring was obtained. Investigation as a host for the complexation of large guest molecules with a suitable convex π-surfaces was accomplished using isothermal NMR binding titrations. Association constants for [6]cycloparaphenylene ([6]CPP), [7]CPP, C₆₀, and C₇₀ were determined.