Two strongly electron-accepting viologens, including an intriguing tricationic species, are reported. The utility of the tricationic viologen for energy storage has been showcased via use as electrode in a proof-of-concept battery.

The synthesis of phosphane-ene photopolymer networks, where the networks are composed of crosslinked tertiary alkyl phosphines are reported. Taking advantage of the rich coordination chemistry of alkyl phosphines, stibino-phosphonium and stibino-bis(phosphonium) functionalized polymer networks could be generated. Small-molecule stibino-phosphonium and stibino-bis(phosphonium) compounds have been well characterized previously and were used as models for spectroscopic comparison to the macromolecular analogues by NMR and XANES spectroscopy. This work reveals that the physical and electronic properties of the materials can be tuned depending on the type of coordination environment. These materials can be used as ceramic precursors, where the Sb-functionalized polymers influence the composition of the resulting ceramic.

In an attempt to address the growing demand for well-defined metallized regions for electronic applications, we developed a new method of forming patterned ceramics. Using UV-curing to synthesize a phosphonium-containing semi-interpenetrating polymer network (S-IPN) followed by ion exchange on the surface with a bis­(phosphino)­borate molybdenum tetracarbonyl complex (2Mo) results in 71% ion exchange of 2Mo to phosphonium sites by attenuated total reflectance infrared (ATR-IR) spectroscopy. The functionalized films were pyrolyzed at temperatures ranging between 800 and 1000 °C to create Mo-containing ceramics. The polymer network can be patterned using electron beam lithography prior to the metal functionalization step. The patterns had good shape retention after metal functionalization and pyrolysis. The polymer networks were characterized using ATR-IR spectroscopy, thermogravimetric analysis, and differential scanning calorimetry, and the swellability and gel content were determined. The resulting ceramics were characterized using optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and powder X-ray diffraction.

Our research group has reported the synthesis of phosphane−ene photopolymer networks, where the networks are composed of cross-linked tertiary alkyl phosphines. Taking advantage of the rich coordination chemistry of alkyl phosphines and the material's susceptibility to solution chemistry, we were able to generate Co, Al, and Ge macromolecular adducts. The metallized polymer networks can be pyrolyzed to make metaldoped carbon, commodity materials in the areas of battery, and fuel cell research. The polymer precursors can also be shaped by spin coating and lithography, before being metallized and pyrolyzed to give patterned ceramics, which display excellent shape retention of the original patterns.