Densely Charged Dodecacationic [3]- and Tetracosacationic Radial [5]Catenanes

Abstract

Summary Here, we report the efficient syntheses of a dodecacationic [3]catenane, which consists of three mechanically interlocked 4+ charged rings despite their mutual Coulombic repulsion, and a tetracosacationic radial [5]catenane, which consists of four 4+ charged rings mechanically interlocked around an 8+ charged ring and bears up to 24 positive charges in its co-constitution. The solid-state structures, determined by single-crystal X-ray crystallography, show that the two mechanical bonds in the [3]catenane result in the nano-confinement of 12 positive charges within a volume of less than 1.65 nm3, corresponding to 7.3 positive charges per nm3, whereas the radial [5]catenane has a charge density of 6.0 positive charges per nm3 and a molecular length of up to 3.7 nm. The template-directed strategy for constructing mechanically interlocked molecules, consisting of multiply charged rings, represents a departure in chemistry tantamount to producing a blueprint for exploring a novel class of organic molecules that boast large numbers and high densities of like charges.