A Strategy for the Construction of Triply Interlocked Organometallic Cages by Rational Design of Poly-NHC Precursors.

ABSTRACT

Three-dimensional (3D) triply interlocked catenanes are a family of chemical topologies that consist of two identical, mechanically interlocked coordination cage components with intriguingly complex structures. Although only a few successful constructions of 3D interlocked catenanes have been achieved to date via metal-mediated assembly, these complex structures have thus far only been targeted by metal-nitrogen/oxygen coordination techniques. Here, taking advantage of rational ligand design, we report the efficient construction of a series of 3D triply interlocked [2]catenanes of the formula [Ag3L2]2, wherein the metal ions exclusively form bonds to N-heterocyclic carbene (NHC) units, and their subsequent transmetalation to the corresponding [Au3L2]2 gold analogues. The formation and transmetalation reactions proceed under mild conditions and are generally applicable. A series of characterization techniques were applied to confirm the formation and structure of the desired 3D triply interlocked architectures multinuclear NMR spectroscopy, ESI-MS, and single-crystal X-ray diffraction analysis. The solid-state structure of [Ag3(1a)2]2(PF6)6 unambiguously confirms the existence of a 3D catenane that consists of two identical, mechanically interlocked trinuclear hexacarbene cage components. The interlocking of two 3D cages into a [2]catenane is driven by the efficient π···π stacking of triazine-triazine stacks with cooperative interactions between imidazo[1,5-a]pyridine subunits. Notably, the triply interlocked organometallic cages exhibit good stability toward various organic solvents, concentrations, and temperatures, and no disassembly occurred in the presence of coronene or pyrene. The future construction of mechanically interlocked architectures using metal-carbene bonds rather than metal-nitrogen bonds may provide assemblies with interesting properties for as-yet-unimagined applications in fields such as sensors and molecular electrical conductors.