Two new trifunctional alkene monomers based on the highly modular perfluoropyridine scaffold were synthesized with an aliphatic and an aromatic moiety, 4penten-1-ol and eugenol, respectively. The monomers were the basis for thiol-ene thermoset materials, formulated against a difunctional or trifunctional thiol. Systems based on these novel monomers have a wide range of thermal properties, with glass transition temperatures spanning from -42 °C to 21 °C. Mixed systems obey the Fox equation, and T g s of the mixtures can be tuned to specific values in that range. Thermal degradation temperatures follow a similar trend, with decomposition temperatures ranging from 274 °C to 348 °C in nitrogen with varying compositions having tailorability therein. This new class of semifluorinated thermoset materials with tunable thermal properties has several potential applications within the aerospace industry, such as sealants and coatings, where stability and survivability at high temperatures in harsh environmental conditions are imperative.

High-temperature linear fluoropyridyl silicone-based oils and network elastomers were prepared via hydrosilylation with multifunctional perfluoropyridine (PFP)-based monomers possessing terminally reactive alkenes. Monomers with varying degrees of functionalization were prepared in a scalable manner and in high purity via the facile, regio-selective, nucleophilic aromatic substitution (SNAr) of PFP in good isolated yields. These multi-reactive monomers were polymerized via Pt-catalyzed hydrosilylation with hydride-terminated polydimethylsiloxanes (H-PDMSs) possessing varying degrees of polymerization and cross-linked with the highly functionalized octadimethylhydrosilyl cubic siloxane. These resulting polymers of varying architecture possessed exceptional thermal stability with no onset of degradation up to 430 °C and char yields as high as 62%, under inert pyrolysis conditions when modified with cubic siloxane. Furthermore, by nature of the aliphatic or aromatic content, programmable glass transition temperatures were achieved from these elastomeric materials. Finally, the linear 3,5,6-fluoropyridine PDMS systems demonstrated the ability to undergo regio-controlled post-functionalization via SNAr with 4-bromophenol, allowing access to silicone oils with potentially tailorable properties for desired applications.

The role of hydrogen bonding in the crystal packing of a series of 4-aminoperfluoropyridines was studied using single-crystal X-ray crystallography. The aminoperfluoropyridines were synthesized using only excess amine to serve as both nucleophile and base. Instead of addition to the perfluoropyridine ring, a strong N–H···F–C hydrogen bond led to cocrystal formation of perfluoropyridine with sterically hindered amines dicyclohexylamine as well as 2-methylpiperdine. This formation is, to our knowledge, the first report of two nonreacting liquids, consisting of only discrete small molecules, combining to form a cocrystalline solid stable under ambient conditions. Perfluoropyridine is stabilized in the crystal lattice approximately 100 °C above its normal boiling point.