An iterative synthetic route for obtaining symmetric polyynes was developed, consisting of a series of iodination and Stille coupling reactions. The starting materials employed in this pathway are simple and can be prepared easily. Polyynes containing up to seven C≡C bonds were synthesized using this method. This route is particularly effective for accessing polyynes with an odd number of C≡C bonds and has allowed for the synthesis of a new iodine‐capped polyyne, diiododecapentayne.

CONSPECTUS: Conjugated carbon-rich materials have drawn much academic and industrial attention in recent years, due to their intriguing electronic and optical properties and potential applications including organic photovoltaics, flexible and wearable electronics, and chemical and biological sensors. Unsaturated carbon−iodine compounds, mainly the derivatives of iodoalkenes and iodoalkynes, are a class of molecules in which iodine atoms are directly connected to unsaturated carbons. These compounds provide unique advantages in the pursuit of carbon-rich materials, largely due to the Lewis acidity of iodine atoms and the lability of the carbon−iodine bonds. The Lewis acidity and electrophilicity of iodine in unsaturated carbon−iodine compounds make them excellent donors of halogen bonding, which is an attractive interaction between the electrophilic halogen atoms and Lewis basic species. Halogen bonding has emerged as a reliable building block in crystal engineering and supramolecular architectures. In this Account, we illustrate examples of the controlled assembly of diiodopolyynes within host−guest cocrystals that contain oxalamide or urea hosts with appropriate Lewis basic end groups and diiodobutadiyne or diiodohexatriyne guests. Halogen bonding interactions between the host and guest result in an ordered alignment of the diiodopolyynes that allows for a solid-state topochemical polymerization. We have used this approach to prepare poly(diiododiacetylene), PIDA, and poly(iodoethynyliododiacetylene), PIEDA, two conjugated polymers composed only of carbon and iodine. In addition, the polarity of the carbon−iodine bond gives unsaturated carbon−iodine compounds an electron-rich π-system, permitting electrophilic addition reactions with molecular halogens. The halogenated products of these additions can then serve as precursors to other conjugated carbon-rich systems. The lability of the carbon−iodine bond, together with the polarizability of iodine and the higher electronegativity of sp-and sp 2hybridized carbons, open up further possibilities in pursuing novel carbon nanomaterials from unsaturated carbon−iodine compounds. For example, we have developed an iterative method for the synthesis of longer symmetric polyynes from shorter diiodopolyynes, using Stille coupling to the iodine-capped polyynes. The iodination/coupling cycle symmetrically lengthens the polyyne chain by two carbon−carbon triple bonds. This method is particularly helpful for preparing polyynes with an odd number of carbon−carbon triple bonds. In addition, the lability of the carbon−iodine bonds of PIDA leads to facile carbonization by pyrolysis or laser irradiation. More strikingly, diiodoalkenes undergo quantitative elimination of iodine in the presence of Lewis bases. This reaction can be used to eliminate iodine at room temperature from PIDA, in which the carbon− iodine bonds are much more easily broken than in the diiodopolyynes, resulting in graphitic carbon materials.