Mesoporous silica monoliths were prepared by the sol-gel technique and filled with 1-ethyl-3-methyl imidazolium [Emim]-X (X=dicyanamide [N(CN)2], ethyl sulfate [EtSO4], thiocyanate [SCN], and triflate [TfO]) ionic liquids (ILs) using a methanol-IL exchange technique. The structure and behavior of the ILs inside the silica monoliths were studied using X-ray scattering, nitrogen sorption, IR spectroscopy, solid-state NMR, and thermal analysis. DSC finds shifts in both the glass transition temperature and melting points (where applicable) of the ILs. Glass transition and melting occur well below room temperature. There is thus no conflict with the NMR and IR data, which show that the ILs are as mobile at room temperature as the bulk (not confined) ILs. The very narrow line widths of the NMR spectra suggest that the ILs in our materials have the highest mobility reported for confined ILs so far. As a result, our data suggest that it is possible to generate IL/silica hybrid materials (ionogels) with bulk-like properties of the IL. This could be interesting for applications in, e.g., the solar cell or membrane fields.

We have synthesized mesoporous silica monoliths functionalized with 2-(4-pyridylethyl)triethoxysilane 1 and N,N-dimethyl-pyridine-4-yl-(3-triethoxysilyl-propyl)-ammonium iodide 2. The organically modified silica monoliths were characterized via IR spectroscopy, nitrogen sorption, small angle X-ray scattering (SAXS), thermogravimetric analysis-differential thermal analysis (TGA-DTA), and acid-base titration. The degree of functionalization can be changed by the ratio of the functional silane to the silica precursor tetramethyl orthosilicate (TMOS). The functionalized silica monoliths were filled with 1-ethyl-3-methyl imidazolium [Emim]-X (X = dicyanamide [N(CN)2] or triflate [TfO]) ionic liquids (ILs) using an established methanol-IL exchange technique. The phase behavior of the resulting ionogels was investigated via differential scanning calorimetry (DSC). DSC curves show that the modification of the silica pore walls with organic groups strongly affects the phase behavior of the confined ILs. Modification with silane 1 completely suppresses the glassy state of [Emim][TfO] previously observed in unmodified silica monoliths (Göbel et al., Phys. Chem. Chem. Phys. 2009, 11, 3653). In contrast, modification with silane 2 leads to the appearance and disappearance, respectively, of a presumed additional phase in [Emim][TfO] and [Emim][N(CN)2] with varying degree of monolith functionalization. The data thus show that organic modification of silica matrix materials could be a viable approach for the tuning of ionogel properties.

331 977 5773. Single-crystal X-ray structure analyses for [PmimSO 3 H][PTS]: Details of the crystal data, data collection and refinement are given in Table S1. The diffraction intensities were collected with graphite-monochromatized Mo Kα radiation. Data collection and cell refinement were carried out using a Bruker Kappa X8 APEX II diffractometer. The temperature of the crystal was maintained at the selected value (200K) by means of a 700 series Cryostream cooling device to within an accuracy of ±2 K. Intensity data were corrected for Lorenz-polarization and absorption factors. The structures were solved by direct methods using SHELXS-97 1 and refined against F 2 by full-matrix least-squares methods using SHELXL-97 2 with anisotropic displacement parameters for all non-hydrogen atoms.All calculations were performed by using the Crystal Structure crystallographic software package WINGX. 3 The structure was drawn using ORTEP3. 4 All hydrogen atoms were located on a differenceFourier map and introduced into the calculations as a riding model with isotropic thermal parameters.

The surface modification of mesoporous silica monoliths through thiol-ene chemistry is reported. First, mesoporous silica monoliths with vinyl, allyl, and thiol groups were synthesized through a sol-gel hydrolysis-polycondensation reaction from tetramethyl orthosilicate (TMOS) and vinyltriethoxysilane, allyltriethoxysilane, and (3-mercaptopropyl)trimethoxysilane, respectively. By variation of the molar ratio of the comonomers TMOS and functional silane, mesoporous silica objects containing different amounts of vinyl, allyl, and thiol groups were obtained. These intermediates can subsequently be derivatized through radical photoaddition reactions either with a thiol or an olefin, depending on the initial pore wall functionality, to yield silica monoliths with different pore-wall chemistries. Nitrogen sorption, small-angle X-ray scattering, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis, and redox titration demonstrate that the synthetic pathway influences the morphology and pore characteristics of the resulting monoliths and also plays a significant role in the efficiency of functionalization. Moreover, the different reactivity of the vinyl and allyl groups on the pore wall affects the addition reaction, and hence, the degree of the pore-wall functionalization. This report demonstrates that thiol-ene photoaddition reactions are a versatile platform for the generation of a large variety of organically modified silica monoliths with different pore surfaces.

Mesoporous carbon/iron carbide hybrid materials with surface areas reaching 800 m 2 g 21 were synthesized via an exotemplating route using monolithic mesoporous silica as template and the ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III) [Bmim][FeCl 4 ] as carbon and iron source. After heat treatment (750 uC under argon) of the [Bmim][FeCl 4 ] precursor confined within the silica matrix, the silica exotemplate was removed with HF leaving the mesoporous C/Fe 3 C hybrid behind. The surface areas and the pore sizes depend on the exotemplate and the surface areas a significantly larger than any other surface area reported for C/Fe 3 C hybrid materials so far. The approach is thus a prototype for the synthesis of high-surface area iron carbide-based hybrid materials with potential application in catalysis.