An array of highly fluorinated polymerizable phosphonium salts (HFPPS) were synthesized from PH3 and utilized in UV‐curable formulations. Inclusion of these salts at very low loading (0.1–1 wt %) into hexanediol diacrylate (HDDA) resulted in hydrophobic surfaces. The water repellency was achieved with short C4F9 fluorocarbon appendages in the monomer as opposed to the bioaccumulative C8F17 appended polymers. The physical properties of these new monomers were also characterized. The molecular architecture of the monomers had a pronounced effect on both their physical properties along with the degree of hydrophobicity imparted in the polymer. Salts utilizing the bis(trifluoromethylsulfonyl)imide anion displayed excellent compatibility with HDDA, while the chloride salts were insoluble. Time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) confirmed the presence of the HFPPS at the surface of the polymer coating. For the first time this demonstrates how these salts may be used to functionalize the surface of a UV‐cured film with ionic species. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2782–2792

The synthesis, characterization, and pyrolysis of a novel class of highly-metallized, redox-active polyelectrolytes that employ phosphorus as a scaffold for the installation of transition metals is described.

The first anion with four polymerizable groups has been synthesized and used to produce durable, crosslinked polyelectrolyte (PE) coatings in a single step. Sodium tetrakis(4‐vinylphenyl)borate (NaBSty4) was produced by the reaction of BCl3 and the Grignard of 4‐bromostyrene. The full series of borates NaBPhxSty4−x, x = 1−3, were also synthesized analogously by reaction of the styryl‐Grignard and PhBCl2, Ph2BCl, or Ph3B. Anion exchange of the borates with tributyl 4‐vinylbenzylphosphonium chloride gave a family of organic salts developed for applications in photopolymerized coatings. The percent UV cure of the polymer films was determined by infrared spectroscopy and this relative level of curing was corroborated by differential scanning calorimetry analysis. The degree of crosslinking imparted to the polymer films by the different monomers has resulted in varied mechanical properties, which were probed by diamond tip scratch tests and nanoindentation. These clearly demonstrated that as the number of polymerizable groups increased, the film hardness increased correspondingly. The final hardness of the films exceeds those of other related systems and identifies styryl borates as viable crosslinking additives in UV curable technologies, especially in the production of durable PE films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

A series of ruthenium and osmium complexes containing highly fluorous diphosphine ligands (F)P(wedge)P(F) = (F(13)C(6)C(6)H(4)-p)(2)P(CH(2))(2)P(p-C(6)H(4)C(6)F(13))(2) (dfppe) and (F(13)C(6)C(6)H(4)-p)(2)P(CH(2))(3)P(p-C(6)H(4)C(6)F(13))(2) (dfppp) has been prepared. The fluorous diphosphine ligands incorporate four C(6)F(13) "fluoro-ponytails", and these have been effective in solubilizing the complexes in supercritical carbon dioxide (scCO(2)). Precise solubility measurements in scCO(2) were performed for some of the complexes. The new complexes [MX(2)((F)P(wedge)P(F))(2)] and [MX((F)P(wedge)P(F))(eta-C(5)H(5))], M = Ru, Os, X = Cl, Br, have been characterized by a number of spectroscopic techniques and their electrochemical properties measured, three of the ruthenium complexes also being characterized by single-crystal X-ray studies. The noncovalent interactions observed in the X-ray structures have been analyzed by the Hirshfeld surface approach, putting them on a more solid footing. The fluorinated complexes show significantly different solvation properties from those of the analogous unfluorinated compounds, particularly with respect to their behavior in common organic solvents and their good scCO(2) solubility.

A variety of Group 10 metal complexes [MXY(dfppp)], M = Ni, X, Y = Cl, Br, M = Pd, Pt, X, Y = Cl or CH(3), containing the recently reported highly fluorous diphosphine ligand, dfppp, 1,3-bis[di(fluoroponytail)phosphino]propane, {(p-F(13)C(6)C(6)H(4))(2)P}(2)(CH(2))(3) have been synthesised. They have been characterised by NMR, mass spectrometry and microanalysis, with two platinum complexes, [PtCl(2)(dfppp)] and [PtClMe(dfppp)], structurally characterised by single crystal X-ray diffraction studies. The highly fluorous nature of the ligands affords the complexes good supercritical CO(2) solubility as measured by supercritical fluid extraction (SFE), and has allowed for the copolymerisation of CO and ethylene using [PdClMe(dfppp)] as the catalyst precursor and CO(2) as the solvent. Additionally, PtCl(2) complexes of the new ligands dfppb, {(p-F(13)C(6)C(6)H(4))(2)P}(2)(CH(2))(4), and dfpop, {(p-F(13)C(6)C(6)H(4)O)(2)P}(2)(CH(2))(3), have also been prepared and characterised.