A series of UV active benzophenone ([CHCOCH-O-(CH)-NMeR][X]; 4, R = CH, n = 3, X = Br; 5a-c, R = CH, n = 3, X = Cl, Br, I; 6a-c, R = CH, n = 4, X = Cl, Br, I; 7a-c, R = CH, n = 6, X = Cl, Br, I) terminated C and C quaternary ammonium salts (QACs) were prepared by thermal or microwave-driven Menshutkin protocols of the appropriate benzophenone alkyl halide (1a-c, 2a-c, 3a-c) with the corresponding dodecyl- or octadecyl N,N-dimethylamine. All new compounds were characterized by NMR spectroscopy, HRMS spectrometry, and, in one instance (4), by single-crystal X-ray crystallography. Representative C and C benzophenone QACs were formulated into 1% (w/v) water or water/ethanol-based aerosol spray coatings and then UV-cured onto plastic substrates (polypropylene, polyethylene, polystyrene, polyvinyl chloride, and polyether ether ketone) with exposure to low to moderate doses of UV (20-30 J cm). Confirmation as to the presence of the coatings was detected by advancing water contact angle measurements, which revealed a more hydrophilic surface after coating. Further confirmation was gained by X-ray photoelectron spectroscopy analysis, time of flight secondary ion mass spectrometry, and bromophenol blue staining, all of which showed the presence of the attached quaternary ammonium molecule. Analysis of surfaces treated with the C benzophenone 5b by atomic force microscopy and surface profilometry revealed a coating thickness of ∼350 nm. The treated samples along with controls were then evaluated for their antimicrobial efficacy against Gram-positive (Arthrobacter sp., Listeria monocytogenes) and Gram-negative (Pseudomonas aeruginosa) bacteria at a solid/air interface using the large drop inoculum protocol; this technique gave no evidence for cell adhesion after a 3 h time frame. These antimicrobial materials show promise for their use as coatings on plastic biomedical devices with the aim of preventing biofilm formation and preventing the spread of hospital acquired infections.

A series of surface attached silane or benzophenone sulfonamide quaternary ammonium antimicrobials show potent efficacy at solid/air and solid/liquid interfaces.

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.

Tetraarylmethanes and adamantanes are important rigid covalent connectors that play a four-way scaffolding role in molecular and materials chemistry. We report the synthesis of a new tetravalent phosphazaadamantane cage, (PNSiMe 3 ) 4 (NMe) 6 (2), that shows high thermal, air, and redox stability due to its geometry. It nevertheless participates in covalent four-fold functionalization reactions along its periphery. The combination of a robust core and reactive corona makes 2 a convenient inorganic scaffold upon which tetrahedral molecular and macromolecular chemistry can be constructed. This potential is demonstrated by the synthesis of a tetrakis(bis(phosphine)iminium) ion (in compound 3) and the first all P/N poly(phosphazene) network (5).

Planar bismuth compounds exhibit tunable Lewis acidity and high catalytic activity for lactone polymerization.

Tetraarylmethanes and adamantanes are important rigid covalent connectors that play a four‐way scaffolding role in molecular and materials chemistry. We report the synthesis of a new tetravalent phosphaza‐adamantane cage, (PNSiMe3)4(NMe)6 (2), that shows high thermal, air, and redox stability due to its geometry. It nevertheless participates in covalent four‐fold functionalization reactions along its periphery. The combination of a robust core and reactive corona makes 2 a convenient inorganic scaffold upon which tetrahedral molecular and macromolecular chemistry can be constructed. This potential is demonstrated by the synthesis of a tetrakis(bis(phosphine)iminium) ion (in compound 3) and the first all P/N poly(phosphazene) network (5).

Thermally robust UV-curable phosphoniums can be utilized as chemically bound surface coatings or as additives in extruded plastics to create an antimicrobial shield on high contact surfaces.

A library of precursor and functionally active quaternary ammonium cations (QACs) for use as corrosion resistant and or antimicrobial coatings, or alternatively as polymer modifiers, is described. High yielding and improved routes to a series of functionally terminated allyl ([(CH2=CH‐CH2)m‐N+(Me)n‐C18H37][X−], 1: m=1, n=2, X−=Br−, 3: m=2, n=1, X−=I−, 4: m=3, n=0, X−=Br−) vinyl ([CH2=CHCH2CH2‐N+Me2‐C18H37][Br−] 5), hydroxy ([HO‐(CH2)m‐N+Me2‐C18H37][Br−], 6: m=3, 7: m=4), haloalkyl ([X1‐(CH2)3‐N+Me2‐C18H37][X−] 8: X1=Br, X=Br−, 9: X1=Cl, X=I−), dimethoxyphenethyl ([(MeO)2C6H3(CH2)2‐N+Me2‐C18H37][Br−], 11), acetamido ([H3C(O)NH‐(CH2)3‐N+Me2‐C18H37][Cl−], 12) cyano ([N≡C–CH2‐N+Me2‐C18H37][Cl−], 13), organocarbonylamino ([R‐C(O)2NH‐(CH2)3‐N+Me2‐C18H37][Br−], 14: R=t‐Bu‐, 15: R=PhCH2‐), phthalimido ([PhthN‐(CH2)3‐N+Me2‐C18H37][Br−], 16), amino ([H2N‐(CH2)3‐N+Me2‐C18H37][Br−] 17), acetylthio ([HC(O)S‐(CH2)3‐N+Me2‐C18H37][Cl−], 18), thiol ([HS‐(CH2)3‐N+Me2‐C18H37][Cl−] 19), disulfa ([‐S‐(CH2)2‐N+Me2‐C18H37]2[Br−]2, 20) C18 QACs prepared by thermal and or microwave driven Menshutkin reactions are detailed. All new compounds were characterized by NMR spectroscopy, HRMS spectrometry and in the case of 1 and 6 by X‐ray crystallography.