Photogenerated lophyl radicals in 1-alkyl-3-vinylimidazolium bis(trifluoromethylsulfonyl)imides.

1-Alkyl-3-vinylimidazolium bis(trifluoromethylsulfonyl)imides were investigated as a matrix for photogenerated lophyl radicals obtained by irradiation of o-chlorohexaarylbisimidazole (o-Cl-HABI). Photoinduced polymerization of ionic liquid monomers using the photoinitiator system composed of o-Cl-HABI and 3-mercapto-1,2,4-4H-triazole was investigated by photo-DSC. Selected thermal properties and viscosity of these ionic liquid monomers are important to understand the lophyl radical kinetics after exposure. Solvent cage effects and viscosity of the ionic liquid monomers strongly affect radical recombination in the dark. This was investigated at different temperatures. The rate constant for radical recombination (krec) decreases from the methyl to the butyl substituted ionic liquid monomer. This may be attributed to an increasing viscosity with increasing size of the alkyl substituent. However, further increase in the size of the alkyl substituent from a butyl to a heptyl group bound at the imidazolium ion results in an increase of krec although the viscosity does further increase. Therefore, a minimum in krec was found for the butyl substituted ionic liquid monomer. Furthermore, the Eyring parameters indicated a dependence on the chain length of the alkyl substituent bound at the imidazolium ion while the activation energy of the viscous flow only slightly changes. Furthermore, the size of the alkyl substituent bound at the cation of the ionic liquid monomers strongly influences both solvent cage and viscosity, and therefore, the concentration of lophyl radicals during photoinduced generation. Photo-induced polymerization of the ionic liquid monomers is affected by viscosity at low conversion and by vitrification at higher conversion. The latter is important for application of the ionic liquid monomers and the polymers made from them by photoinduced polymerization.

Ion transport and softening in a polymerized ionic liquid.

Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this work, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current-voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as the Wien effect). Onsager's theory of the Wien effect coupled with the Poisson-Nernst-Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. The observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field.

Extended mechanistic aspects on photoinitiated polymerization of 1,6-hexanediol diacrylate by hexaarylbisimidazoles and heterocyclic mercapto compounds.

Chlorine substituted hexaarylbisimidazole (o-Cl-HABI) efficiently initiates radical polymerization of multifunctional acrylic esters in the presence of a heterocyclic mercapto compound if the latter can form its tautomeric thione. Exposure of o-Cl-HABI results in lophyl radicals, which efficiently add to the thione in the first step while the second step releases a highly reactive thiyl radical from this intermediate. LC-MS and CID-MS measurements support this reaction scheme. Furthermore, photo-DSC experiments applying UV light between 320 and 380 nm showed that mercaptotriazole and phenylmercaptotriazole exhibited the best reactivity in the monomer 1,6-hexanediol diacrylate (HDDA) while alkyl substituted mercaptotriazoles showed less reactivity. Change of the triazole heterocycle by mercaptoimidazole resulted in a significant decrease of photoinitiation efficiency. This heterocycle does not form the corresponding thione in HDDA as shown by NMR measurements. Replacement of mercaptotriazole by an alkylthiol leads to a system showing the lowest photoinitiation efficiency in this series. Formation of thione structure in the case of heterocyclic mercapto compounds may cause higher reactivity of the heterocyclic mercapto compounds with the lophyl radical in the monomer chosen.

Recombination of lophyl radicals in pyrrolidinium-based ionic liquids.

The recombination of photolytically generated lophyl radicals has been investigated by UV/Vis spectroscopy in 1-alkyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides (NTf2) in comparison with 1-butyl-3-methylimidazolium NTf2 , dimethyl sulfoxide, and triacetin. The 1-alkyl-1-methylpyrrolidinium-based ionic liquids contain an alkyl substituent varying between butyl and decyl groups. Optically pure ionic liquids are used in these studies. Temperature-dependent investigation of lophyl radical recombination shows an increase in the radical recombination rate with increasing temperature in each solvent, which is caused by decreasing viscosity with increasing temperature. Furthermore, the viscosity of the 1-alkyl-1-methylpyrrolidinium NTf2 increases nearly linearly within the row of these ionic liquids. In contrast, the recombination of the photolytically generated lophyl radicals is significantly faster in the ionic liquids than in the traditional organic solvents under investigation. Moreover, the recombination rate increases with the length of the alkyl chain bound at the cation of the ionic liquid at a given temperature. This may be caused by an increase in the extent of lophyl radical recombination within the solvent cage. Solvent cage effects dominate in the case of lophyl radical recombination in ionic liquids bearing a long alkyl chain or if the temperature is near the melting temperature of the ionic liquid. The positive value of the activation entropy supports this hypothesis. The results obtained are important for discussion of bimolecular radical reactions in ionic liquids.