A Robust, Divalent, Phosphaza-bicyclo[2.2.2]octane Connector Provides Access to Cage-Dense Inorganic Polymers and Networks

While polymers containing chain or ring motifs in their backbone are ubiquitous, those containing well-defined molecular cages are very rare and essentially unknown for the inorganic elements. We report that a rigid and dinucleophilic cage (PNSiMe3)2(NMe)6, which is chemically robust and accessible on a multi-gram scale from commercial precursors, serves as a linear and divalent connector that forms cage-dense inorganic materials. Reaction of the cage with various ditopic P­(III) dihalide comonomers proceeded via Me3SiCl elimination to give high molecular weight (30 000–70 000 g mol–1), solution-processable polymers that form free-standing films. The end groups of the polymers could be tuned to engender orthogonal reactivity and form block copolymers. Networked cage-dense materials could be accessed by using PCl3 as a tritopic P­(III) linker. Detailed mechanistic studies implicate a stepwise polycondensation that proceeds via phosphino–phosphonium ion intermediates, prior to Me3SiCl loss. Thus, metathesis between the dinucleophilic cage and polyhalides represents a general strategy to making cage-dense polymers, setting the stage for systematically understanding the consequences of the three-dimensional microstructure on macroscopic material properties.