Unlocking Acyclic π‑Bond Rich Structure Space with Tetraethynylethylene–Tetravinylethylene Hybrids

Literature reports describe tetraethynylethylene (TEE) as unstable but tetravinylethylene (TVE) as stable. The stabilities of these two known compounds are reinvestigated, along with those of five unprecedented TEE-TVE hybrid compounds. The five new C10 hydrocarbons possess a core, tetrasubstituted CC bond carrying all possible combinations of vinyl and ethynyl groups. A unified strategy is described for their synthesis, whereupon cross-conjugated ketones are dibromo-olefinated then cross-coupled. Due to an incorrect but nonetheless widely held belief that acyclic π-bond rich hydrocarbons are inherently unstable, a standardized set of robustness tests is introduced. Whereas only TVE survives storage in neat form, all seven hydrocarbons are remarkably robust in dilute solution, generally surviving exposure to moderate heat, light, air, and acid. The first X-ray crystal structure of TEE is reported. Subgroups of hybrids based upon conformational preferences are identified through electronic absorption spectra and associated computational studies. These new acyclic π-bond rich systems have extensive, untapped potential for the production of stable, conjugated carbon-rich materials.