Presented is an economical means of removing fluorine from various highly fluorinated arenes using NaBH4. The procedure was adapted for different classes of perfluoroarenes. A novel isomer of an emerging class of organic dyes based on the carbazole phthalonitrile motif was succinctly synthesized in two steps from tetrafluorophthalonitrile, demonstrating the utility of the hydrodefluorination procedure. Initial exploration of the dye shows it to be photoactive and capable of facilitating contrathermodynamic styrenoid E/Z isomerization.

Current methods of urethane preparation from amines invariably involve high-energy and often toxic or cumbersome molecules to make the process exergonic. CO 2 aminoalkylation using olefins and amines represents an attractive albeit endergonic alternative. We report a moisture-tolerant method that uses visible light energy to drive this endergonic process (+25 kcal/mol at STP) using sensitized arylcyclohexenes. They convert much of the photon's energy to strain upon olefin isomerization. This strain energy greatly enhances alkene basicity, allowing for sequential protonation by and interception of ammonium carbamates. Following optimization steps and amine scope evaluation, an example product arylcyclohexyl urethane underwent transcarbamoylation with some demonstrative alcohols to form more general urethanes with concomitant regeneration of the arylcyclohexene. This represents a closure of the energetic cycle, producing H 2 O as the stoichiometric byproduct.

Ion-pair comonomers (IPCs) where both the anion and cation contain polymerizable functional groups offer a route to prepare polyampholyte, ion-containing polymers. Polymerizing vinyl functional groups by free-radical polymerization produces bridging ion-pairs that act as non-covalent crosslinks between backbone segments. In particular the homopolymerization of the IPC vinyl benzyl tri-n-octylphosphonium styrene sulfonate produces a stiff, glassy polymer with a glass transition temperature (Tg) of 191 °C, while copolymerization with a non-ionic acrylate produces microphase separates ionomers with ion-rich and ion-poor domains. This work investigates the tuning of the Tg of the polyelectrolyte or ion-rich domains of the ionomers by copolymerizing with vinyl benzyl tri-n-octylphosphonium p-toluene sulfonic acid. This chemically similar repeat unit with pendant rather than bridging ion-pairs lowers the Tg compared to the polyelectrolyte or ionomer containing only the IPC segments. Rheological measurements were used to characterize the thermomechanical behavior and Tg of different copolymers. The Tg variation in the polyelectrolyte vs. weight fraction IPC could be fit with either the Gordon–Taylor or Couchman–Karasz equation. Copolymerization of IPC with a chemically similar cationic monomer offers a viable route to systematically vary the Tg of the resulting polymers useful for tailoring the material properties in applications such as elastomers or shape memory polymers.