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.

Most studies in molecular electronics focus on altering the molecular wire backbone to tune the electrical properties of the whole junction. However, it is often overlooked that the chemical structure of the groups anchoring the molecule to the metallic electrodes influences the electronic structure of the whole system and, therefore, its conductance. We synthesised electron-accepting dithienophosphole oxide derivatives and fabricated their singlemolecule junctions. We found that the anchor group has a dramatic effect on charge-transport efficiency: in our case, electron-deficient 4-pyridyl contacts suppress conductance, while electron-rich 4-thioanisole termini promote efficient transport. Our calculations show that this is due to minute changes in charge distribution, probed at the electrode interface. Our findings provide a framework for efficient molecular junction design, especially valuable for compounds with strong electron withdrawing/donating backbones.

The reductive dehalogenation of a zwitterionic GeII species to make a zwitterionic GeI dimer with a 1,2‐dicationic core is reported herein. To the root of the stability of this compound, the molecular and electronic structures were comprehensively characterized and investigated using crystallographic, spectroscopic, and computational methods. It was determined that the Ge centers are attracted because they are both electron‐rich and positively charged. A comparison to the electronic structure in triphosphenium cations revealed varying degrees of covalent bonding and that this difference can be distinguished spectroscopically.

The development of batteries and fuel cells has brought to light an eed for carbon anode materials doped homogeneously with electrocatalytic metals.I np articular, combinations of electrocatalysts in carbon have shown promising activity.Am ethod to derive functional carbon materials is the pyrolysis of metallopolymers. This work describes the synthesis of ab ifunctional phosphonium-based system derived from ap hosphane-ene network. The olefin functionality can be leveraged in ah ydrogermylation reaction to functionalize the materialw ithG e. Unaffected by this radicala ddition, the bromide counterion of the phosphonium cation can be used to subsequently incorporate a second metal in an ion-complexation reactionw ithC uBr 2. The characterization of the polymers and the derived ceramics are discussed.

In this work, we show that polymer networks composed of tertiary alkyl phosphines can be cleanly functionalized with phosphino‐phosphonium or triphosphenium cations. Methods for functionalizing the polymers range from halide abstraction of commercially available reagents, to ligand exchange from simple to make reported compounds, and finally, macromolecular ligand design guided by observations made at the molecular level to accommodate the formation of kinetically favored triphosphenium cation functionalized networks. The synthesis, comprehensive characterization, and comparison of the new polymers to molecular analogues is outlined. It is shown the addition of the low valent phosphorus centers to the polymer network has the effect of tuning material physical properties.