Polythioethers by thiol-ene click polyaddition of α,ω-alkylene thiols.

The straightforward synthesis of a series of poly(thioether)s by photoinduced thiol-ene click polyaddition of α,ω-alkylene thiols is reported. It is found that linear and telechelic poly(thioether)s can be directly obtained from α,ω-alkylene thiols with, for example, alkyl chain length of m = 1,2,3, and 9. The reaction proceeds without additives such as (radical) initiators or metal compounds and can simply be carried out by UV-irradiation of the bulk monomer or monomer solution. Ex situ kinetic studies reveal that the reaction proceeds by a typical a step-growth polyaddition mechanism. As the homologue series of poly(thioether)s are now synthetically accessible, new direct pathways to tailored poly(alkyl sulphoxide)s and poly(alkyl sulfone)s are now possible.

Novel non-conjugated main-chain hole-transporting polymers for organic electronics application.

A new class of hole-transporting polymers for use in organic electronic devices such as organic light-emitting diodes (OLEDs) or photorefractive holographic storage devices has been synthesized. The polymers contain tetraarylbenzidines or tetraarylphenylenediamines as charge-transporting units in the polymer backbone and are connected by non-conjugating fluorene bridges. For use in OLEDs the novel polymers were functionalized with oxetane groups that can be cross-linked via a cationic ring opening polymerization to yield insoluble networks. Such insoluble films are necessary for the fabrication of multilayer devices by wet deposition techniques. The novel materials feature improved film-formation properties as demonstrated in green-emitting double-layer OLEDs.

Ring-Opening Metathesis Polymerization of Nitrile Substituted cis-Cyclooctenes.

New nitrile-containing polymers have been synthesized by ring-opening metathesis polymerization of cis-cyanocyclooct-4-ene and cis-1,2-dicyanocyclooct-5-ene with a 2(nd) generation Grubbs catalyst [(H(2) IMes)(PCy(3) )Cl(2) Ru = CHPh] (H(2) IMes = N,N'-bis(mesityl)-4,5-dihydroimidazol-2-ylidene). With increasing content of nitrile moieties on the cyclooctene ring the reaction rates decrease from cis-cyclooctene to cis-cyanocyclooct-4-ene and cis-1,2-dicyanocyclooct-5-ene. Contrary to commercially available nitrile rubbers (unhydrogenated and hydrogenated butadiene/acrylonitrile copolymers) in which double bonds, nitrile moieties, and methylene bridges are randomly distributed along the main chain, the new polymers show a regular distribution of structural entities.

Solvent-ligated copper(II) complexes for the homopolymerization of 2-methylpropene.

Copper(II) complexes with weakly coordinating counter anions can be utilized as highly efficient catalysts for the synthesis of poly(2-methylpropene) ("polyisobutene") with a high content of terminal double bonds. These copper(II) compounds are significantly more active than the manganese(II) complexes described previously, can be applied in chlorine-free solvents such as toluene, are easily accessible, and can be handled at room temperature and in laboratory atmospheres for brief periods, but they are sensitive to excess water, thereby losing their catalytic activity. Replacing the acetonitrile ligands by benzonitrile ligands improves the solubility and catalytic activity in nonpolar and nonchlorinated solvents. However, the benzonitrile copper(II) compounds have lower thermal stability than their acetonitrile congeners.

Neutron reflectometry and spectroscopic ellipsometry studies of cross-linked poly(dimethylsiloxane) after irradiation at 172 nm.

Poly(dimethylsiloxane) (PDMS) was irradiated under ambient conditions in air with a Xe2-excimer lamp. The formation of atomic oxygen and ozone during irradiation in air by V-UV photons results in the transformation of PDMS to silicon oxide. The irradiated surfaces were studied by spectroscopic ellipsometry and neutron reflectometry. The measurements revealed the formation of a rough, i.e., between 11 and 20 nm, oxidized surface layer and a decrease of the total layer thickness. The thickness of the oxidized layer decreased for a given PDMS thickness when the polymer was irradiated for longer times and/or higher intensities. The composition of the oxidized layer after irradiation was not uniform through the layer and consisted of a mixture of original polymer and silicon bonded to three or four oxygen atoms (SiOx). The refractive index n determined by ellipsometry reaches a value similar to values reported for SiO2.

Novel ruthenium-based metathesis catalysts containing electron-withdrawing ligands: synthesis, immobilization, and reactivity.

The syntheses and reactivity of seven different ruthenium-based metathesis catalysts are described. Ru(CF3COO)2(PCy3)(=CH-2-(2-PrO)C6H4) (1), Ru(CF3COO)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (2), and Ru(CF3COO)2(PCy(3))(1,3-dimesityldihydroimidazolin-2-ylidene)(=CHC6H5) (3) were prepared via chlorine exchange by reacting RuCl2(PCy3)2(=CH-2-(2-PrO)C6H4), RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4), and RuCl2(PCy3)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CHC6H5), respectively, with silver trifluoroacetate (Cy =cyclohexyl). In analogy, Ru(CF3CF2COO)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (4) and Ru(CF3CF2CF2COO)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (5) were prepared from RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) via reaction with CF3CF2COOAg and CF3CF2CF2COOAg, respectively. Ru(C6F5COO)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (6) and Ru(C6F5O)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (7) were prepared from RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) via reaction with C6F5COOTl and C6F5OTl, respectively. Supported catalysts Ru(PS-DVB-CH2OOCCF2CF2CF2COO)(CF3COO)(PCy3)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CHC6H5) (8), Ru(PS-DVB-CH2OOCCF2CF2CF2COO)(CF3COO)(PCy3)(=CH-2-(2-PrO)C6H4) (9), and Ru(PS-DVB-CH2OOCCF2CF2CF2COO)(CF3COO)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (10) were synthesized by reaction of RuCl2(PCy3)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CHC6H5), RuCl2(PCy3)(=CH-2-(2-PrO)C6H4), and RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4), respectively, with a perfluoroglutaric acid-derivatized poly(styrene-co-divinylbenzene) (PS-DVB) support (silver form). Halogen exchange in PCy3-containing systems had to be carried out in dichloromethane in order to suppress precipitation of AgCl.PCy3. The reactivity of all new catalysts in ring-closing metathesis (RCM) of hindered electron-rich and -poor substrates, respectively, at elevated temperature (45 degrees C) was compared with that of existing systems. Diethyl diallylmalonate (DEDAM, 11), diethyl allyl(2-methylallyl)malonate (12), N,N-diallyl-p-toluenesulfonamide (13), N-benzyl-N-but-1-en-4-ylbut-2-enecarboxylic amide (14), and N-allyl-N-(1-carboxymethyl)but-3-en-1-yl-p-toluenesulfonamide (15) were used as educts. Supported catalysts were prepared with high loadings (2.4, 22.1, and 160 mg of catalyst/g PS-DVB for 8, 9, and 10, respectively). Catalyst 8 showed higher and catalysts 9 and 10 sowed significantly reduced activities in RCM compared to their homogeneous analogues. Thus, with 8, turnover numbers (TONs) up to 4200 were realized in stirred-batch (carousel) RCM experiments. To elucidate the nature of the bound species, catalysts 8-10 were subjected to 13C- and 31P-MAS NMR spectroscopy. These investigations provided evidence for the proposed structures. Leaching of ruthenium into the reaction mixture was low, resulting in ruthenium contents <85 ppb (ng/g) in the final RCM-derived products.

Lipopolymers from new 2-substituted-2-oxazolines for artificial cell membrane constructs.

We present the synthesis of novel 2-oxazoline monomers with different 2-substituents and their consecutive conversion into lipopolymers by living cationic polymerization. The side functions of these monomers were varied to realize different steric needs and hydrogen bonding interactions of the polymer side chains. 2-(2'-N-pyrrolidonyl-ethyl)-2-oxazoline, 2-(3'-methoxymonoethyleneglycol)propyl-2-oxazoline, and 2-(3'-methoxytriethyleneglycol)propyl-2-oxazoline were synthesized. All of the monomers could be converted into the corresponding lipopolymers by living cationic polymerization using 2,3-di-O-octadecyl-1-trifluormethansulfonyl-sn-glycerol as the initiator. The characterization of the 2,3-di-O-octadecyl-glycerol-poly(2-oxazoline) lipopolymers by NMR spectroscopy, IR spectroscopy, and gel permeation chromatography revealed that the targeted molar masses and compositions can be controlled by the initial initiator/monomer ([M](0)/[I](0)) ratio for all the synthesized lipopolymers. The polydispersities were found to be narrow (polydispersity indices from 1.06-1.3). The amphiphilic lipopolymers were spread at the air-water interface (Langmuir-Blodgett film balance) and the effect of the polymer side groups and chain lengths upon the Pi-area (A) isotherms of the corresponding lipopolymer monolayers were compared and analyzed. The impact of the polymer side functionalities on a 2D gel formation was examined using an interfacial rheometer operated in an oscillating stress-strain mode. Interestingly enough, none of the newly synthesized lipopolymers showed a rheological transition. This somewhat surprising result not only verified that these 2D gels are not established by hydrogen bonding among hydrophilic polymer moieties, as earlier proposed, but also supported the concept of jammed surface micelles as the more likely origin for the gelation phenomenon. [Diagram: see text]

Solvent-ligated manganese(II) complexes for the homopolymerization of isobutene and the copolymerization of isobutene and isoprene.

Polyisobutenes with a high content of terminal olefinic groups can be synthesized by using manganese(II) initiators in homogeneous solution. These easily accessible complexes initiate the polymerization at room temperature and above, and afford highly reactive, gel-free polyisobutenes with high viscosities. Furthermore, the initiators were successfully used for the copolymerization of isobutene with isoprene. The high activities of the Mn(II) initiators seem to be related to their weakly coordinating nitrile ligands, which are easily displaced by substrate molecules. Replacing the nitrile ligands by other more strongly coordinating ligands such as water reduces the initiator activity significantly. The Mn(II) initiators are surprisingly resistant to temperature.

Factors relevant for the ruthenium-benzylidene-catalyzed cyclopolymerization of 1,6-heptadyines.

Fourteen metathesis initiators that had been designed for use in the living polymerization of diethyl dipropargylmalonate (DEDPM), including the Hoveyda catalyst [RuCl(2)(IMesH(2))([double bond]CH-2-(2-PrO)[bond]C(6)H(4))] (1 a), as well as [Ru(CF(3)COO)(2)(IMesH(2))([double bond]CH-2-(2-PrO)[bond]C(6)H(4))] (1 b), [Ru(CF(3)CF(2)COO)(2)(IMesH(2))([double bond]CH-2-(2-PrO)[bond]C(6)H(4))] (1 c), [Ru(CF(3)CF(2)CF(2)COO)(2)(IMesH(2))([double bond]CH-2-(2-PrO)[bond]C(6)H(4))] (1 d), [RuCl(2)(IMesH(2))([double bond]CH-2,4,5-(MeO)(3)[bond]C(6)H(2))] (2 a), [Ru(CF(3)COO)(2)(IMesH(2))([double bond]CH-2,4,5-(MeO)(3)[bond]C(6)H(2))] (2 b), [Ru(CF(3)CF(2)COO)(2)(IMesH(2))([double bond]CH-2,4,5-(MeO)(3)[bond]C(6)H(2))] (2 c), [Ru(CF(3)CF(2)CF(2)COO)(2)(IMesH(2))([double bond]CH-2,4,5-(MeO)(3)[bond]C(6)H(2))] (2 d), [RuCl(2)(IMes)([double bond]CH-2-(2-PrO)[bond]C(6)H(4))] (3 a), [Ru(CF(3)COO)(2)(IMes)([double bond]CH-2-(2-PrO)[bond]C(6)H(4))] (3 b), [RuCl(2)(IMesH(2))([double bond]CH-2-(2-PrO)-5-NO(2)[bond]C(6)H(3))] (4 a), [Ru(CF(3)COO)(2)(IMesH(2))([double bond]CH-2-(2-PrO)-5-NO(2)[bond]C(6)H(3))] (4 b), [Ru(CF(3)CF(2)COO)(2)(IMesH(2))([double bond]CH-2-(2-PrO)-5-NO(2)[bond]C(6)H(3))] (4 c), and [Ru(CF(3)CF(2)CF(2)COO)(2)(IMesH(2))([double bond]CH-2-(2-PrO)-5-NO(2)[bond]C(6)H(3))] (4 d) (IMes=1,3-dimesitylimidazol-2-ylidene; IMesH(2)=1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) were prepared. Living polymerization systems could be generated with DEDPM by careful tuning of the electronic nature and steric placement of the ligands. Although 1 a, 2 a, 3 a, 3 b, and 4 a were inactive in the cyclopolymerization of DEDPM, and initiators 1 b-d did not allow any control over molecular weight, initiators 2 b-d and 4 b-d offered access to class VI living polymerization systems. In particular, compounds 2 b and 4 d were superior. The livingness of the systems was demonstrated by linear plots of M(n) versus the number of equivalents of monomer added (N). For initiators 2 b-d and 4 b-d, values for k(p)/k(i) were in the range of 3-7, while 1 b, 1 c, and 1 d showed a k(p)/k(i) ratio of >1000, 80, and 40, respectively. The use of non-degassed solvents did not affect these measurements and underlined the high stability of these initiators. The effective conjugation length (N(eff)) was calculated from the UV/Vis absorption maximum (lambda(max)). The final ruthenium content in the polymers was determined to be 3 ppm.

Synthesis and reactivity of homogeneous and heterogeneous ruthenium-based metathesis catalysts containing electron-withdrawing ligands.

The synthesis and heterogenization of new Grubbs-Hoveyda type metathesis catalysts by chlorine exchange is described. Substitution of one or two chlorine ligands with trifluoroacetate and trifluoromethanesulfonate was accomplished by reaction of [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (IMesH(2) = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) with the silver salts CF(3)COOAg and CF(3)SO(3)Ag, respectively. The resulting compounds, [Ru(CF(3)SO(3))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (1), [RuCl(CF(3)SO(3))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (2), and [Ru(CF(3)CO(2))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (3) were found to be highly active catalysts for ring-closing metathesis (RCM) at elevated temperature (45 degrees C), exceeding known ruthenium-based catalysts in catalytic activity. Turn-over numbers (TONs) up to 1800 were achieved in RCM. Excellent yields were also achieved in enyne metathesis and ring-opening cross metathesis using norborn-5-ene and 7-oxanorborn-5-ene-derivatives. Even more important, 3 was found to be highly active in RCM at room temperature (20 degrees C), allowing TONs up to 1400. Heterogeneous catalysts were synthesized by immobilizing [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] on a perfluoroglutaric acid derivatized polystyrene-divinylbenzene (PS-DVB) support (silver form). The resulting supported catalyst [RuCl(polymer-CH(2)-O- CO-CF(2)-CF(2)-CF(2)-COO)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (5) showed significantly reduced activities in RCM (TONs = 380) compared with the heterogeneous analogue of 3. The immobilized catalyst, [Ru(polymer-CH(2)-O-CO-CF(2)-CF(2)-CF(2)-COO)(CF(3)CO(2))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (4) was obtained by substitution of both Cl ligands of the parent Grubbs-Hoveyda catalyst by addition of CF(3)COOAg to 5. Compound 4 can be prepared in high loadings (160 mg catalyst g(-1) PS-DVB) and possesses excellent activity in RCM with TONs up to 1100 in stirred-batch RCM experiments. Leaching of ruthenium into the reaction mixture was unprecedentedly low, resulting in a ruthenium content <70 ppb (ng g(-1)) in the final RCM-derived products.

Amphiphilic polymer supports for the asymmetric hydrogenation of amino acid precursors in water.

This paper describes the synthesis and characterization of a new class of amphiphilic, water-soluble diblock copolymers based on 2oxazoline derivatives with pendent (2S,4S)-4-diphenylphosphino-2-(diphenylphosphinomethyl)pyrrolidine (PPM) units in the hydrophobic block. The synthetic strategy involves the preparation of a diblock copolymer precursor with ester functionalities in the side chain; which were converted into carboxylic acids in a polymer-analogous step and finally reacted with the PPM ligand. The structures of the copolymers were characterized by (1)H and (31)P NMR spectroscopy and GPC measurements. Subsequently, these polymers were successfully utilized as a polymeric support for the asymmetric hydrogenation of 1) (Z)-alpha-acetamido cinnamic acid and 2) methyl (Z)-alpha-acetamido cinnamate in water, showing 90 % substrate conversion at 25 degrees C within 20 minutes at atmospheric H(2) pressure (1 bar) for methyl (Z)-alpha-acetamido cinnamate.

Multi-colour organic light-emitting displays by solution processing.

Organic light-emitting diodes (OLEDs) show promise for applications as high-quality self-emissive displays for portable devices such as cellular phones and personal organizers. Although monochrome operation is sufficient for some applications, the extension to multi-colour devices--such as RGB (red, green, blue) matrix displays--could greatly enhance their technological impact. Multi-colour OLEDs have been successfully fabricated by vacuum deposition of small electroluminescent molecules, but solution processing of larger molecules (electroluminescent polymers) would result in a cheaper and simpler manufacturing process. However, it has proved difficult to combine the solution processing approach with the high-resolution patterning techniques required to produce a pixelated display. Recent attempts have focused on the modification of standard printing techniques, such as screen printing and ink jetting, but those still have technical drawbacks. Here we report a class of electroluminescent polymers that can be patterned in a way similar to standard photoresist materials--soluble polymers with oxetane sidegroups that can be crosslinked photochemically to produce insoluble polymer networks in desired areas. The resolution of the process is sufficient to fabricate pixelated matrix displays. Consecutive deposition of polymers that are luminescent in each of the three RGB colours yielded a device with efficiencies comparable to state-of-the-art OLEDs and even slightly reduced onset voltages.