Polymer Network Formation Using the Phosphane–ene Reaction: A Thiol–ene Analogue with Diverse Postpolymerization Chemistry

Air-stable primary phosphines were photopolymerized using phosphane–ene chemistry, the phosphorus analogue of the thiol–ene reaction, to fabricate a completely new class of polymer networks. It was demonstrated that the tunable thermal and physical properties accessible using thiol–ene chemistry could also be achieved using an analogous phosphane–ene reaction. At the same time, the presence of the 31 P nucleus that is easily observed using NMR spectroscopy allowed the chemical structures of the networks to be directly probed using solid state NMR spectroscopy. Following its incorporation into the network, phosphorus offers the distinct difference and advantage of being able to undergo a diverse array of further derivatization to afford functional materials. For example, the networks were demonstrated to serve as effective oxygen scavengers and to bind transition metals (e.g., Pd). By using the air stable ferrocenyl phosphine (FcCH 2 CH 2 )PH 2, redox-active networks were produced and these materials could be pyrolyzed to yield magnetic ceramics. Overall, this demonstrates the promise of phosphane–ene chemistry as an alternative to thiol–ene systems for providing functional materials for a diverse range of applications.