Fluoropolymers have infiltrated society as coatings and insulators. However, low processability, few opportunities for polymer functionalization, and explosive monomers hampering academic investigation of these materials have precluded the extension of the unique properties of perfluorocarbons to the cutting edge of material science. Here, we present semifluorinated iodo–ene polymers as a scaffold to overcome fluoropolymer limitations. A sodium dithionate initiated polymerization of perfluorodiiodides and dienes allows for high-molecular-weight polymers (>100 kDa) to be prepared in the presence of oxygen and water with up to 59 wt % fluorine content. These conditions are sufficiently mild to enable the polymerization of functional dienes, leading to biodegradable fluoropolymers. The iodo–ene polymerization results in the addition of polarizable iodine atoms, which improve polymer processability; yet, these atoms can be removed after processing for enhanced stability. Displacement of the iodine atoms with thiols or azides facilitates covalent surface modification and cross-linking. Finally, the low bond dissociation energy of the C–I bond allows allyl group addition as well as photo-cross-linking. Collectively, the simple synthesis and modular nature of the semifluorinated iodo–ene polymers will enable the convergence of perfluorocarbons and advanced materials.

Synthesis of semifluorinated polymers containing fluorous groups on the backbone or as side chains is an increasingly popular field of research.

Postpolymerization modifications are a prominent route for tuning polymer properties and diversifying materials. Thus, polymers containing robust chemical handles are desirable. Vinyl iodide functionality is commonly enlisted for selective transformations on small molecules, but these chemistries, while efficient enough for postpolymerization modifications, are less frequently performed on macromolecules due to limited methods to install vinyl iodide groups into polymers. Here, we present an iodo-yne polymerization involving diynes and diiodoperfluoroalkanes to facilely give semifluorinated polymers with vinyl iodide groups throughout the polymer chain. The iodo-yne polymerization yields polymers of at least 6 kDa while open to air in aqueous solvent. We demonstrate that the iodo-yne polymers can be modified at the vinyl iodide functionality via a variety of metal-catalyzed cross-coupling reactions. Additionally, the iodide can be eliminated to give electronically activated alkynes that can undergo cycloaddition with azides. Taken together, this work will push the current boundaries of functional polymers and assist in the development of modernized, smart materials.

A new synthesis of substituted acridines is achieved by palladium-catalyzed addition of terminal acetylenes between the aryl rings of bis(2-bromophenyl)amine. By including a diamine base and elevating the temperature, the reaction pathway favors the formation of acridine over a double Sonogashira reaction to form bis(tolan)amine. This method is demonstrated with several aryl-alkynes and alkyl-alkynes.

Through a combined computational and isotopic labeling study, it has been observed that the activation energy for the aryl–alkyne ring closure of the azaborine containing 4-ethynyl-4a-aza-4b-boraphenanthrene is dramatically lower, and it appears to proceed via an alternate mechanism than that of its hydrocarbon analog. This catalyst-free reaction proceeds at modest reaction conditions compared with traditional pyrolytic synthetic methods and holds promise for the efficient construction of fused ring systems containing azaborine functional groups that may not be accessible in the purely hydrocarbon form.