Conjugated Macrocycles via Metal-Mediated Dynamic Covalent Chemistry

Conjugated macrocycles are of great interest to the chemistry community both as molecular analogs of graphene nanostructures, and for the unique supramolecular and electronic behavior they exhibit. While many structurally diverse macrocycles have been realized, most macrocyclizations are kinetically controlled, requiring high dilution and often affording low yields. Thermodynamically controlled macrocyclization strategies offer a potential solution to these problems, but there are relatively few reversible, C-C bond forming reactions suitable for these purposes. To this end, we have developed a zirconocene-mediated strategy to reversibly couple diynes to form macrocycles and cages with controllable size, shape, and functionality in high yield. We are currently focused on leveraging this versatile synthetic strategy for applications in host-guest chemistry, redox active materials, and sensing/switching.