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Abstract: Two lamellar organosilica films made up of stacks of head-to-head and head-to-tail alkyl bilayers were synthesized by a UV-driven polymerization of n-C18H37SiCl3 and n-C18H37Si(OCH3)3, respectively. In addition to thermogravimetry and small-angle X-ray scattering, the characterization of these multilayer systems was focused on a variety of multinuclear solid-state NMR methods (1H, 29Si, 13C, 2D WISE). The chemical structure of the siloxane interlayer, the alkyl chain conformation and thermal stability were systematically investigated and compared. Through its marked sensitivity to molecular motion, solid-state NMR was used to investigate the effect of interdigitation on alkyl chain dynamics. [Copyright &y& Elsevier]

Abstract: In sol–gel polymerization of alkoxysilane precursors, base catalysts are usually employed to introduce textural properties. Herein, we show the feasibility and interest of a photobase-catalyzed sol–gel reaction to afford silicate films. Our inorganic polymerization is solvent-free, single-step and UV activatable with a mixture of α-aminoacetophenone (photobase generator), benzophenone (photosensitizer) and triphenylphosphine (oxygen scavenger). To date, the present tricomponent photolatent system generating N-alkyl morpholine tertiary amines represents one of the most efficient photobase generators reported so far in sol–gel chemistry. A combination of spectroscopic and electron microscopy techniques enabled to investigate the fundamental chemistry underlying alkoxysilane photopolymerization: reaction mechanism, hydrolysis kinetics and siloxane microstructure. Systematic comparison with a photoacid-catalyzed process revealed also the impact of the photocatalyst nature on film texture, morphology and optical properties. [Copyright &y& Elsevier]

• Solid-state nuclear magnetic resonance (NMR) reveals ordering in hybrid silica film. • Narrower 1H NMR lines reflect a better chemical uniformity of ordered structures. • Narrower 13C NMR lines translate a higher mobility of ordered structures. • Disorder-to-order transition is reflected by 1H transverse relaxation time. In the context of increasing use of nanostructured materials, finding innovative characterization methods able to assess precisely the level of ordering is essential. To this end, a range of model organic-inorganic copolymer-silica films is synthesized using poly(ethylene oxide)- b -poly(propylene oxide)- b -poly(ethylene oxide) amphiphilic triblock copolymer as supramolecular template. Upon increasing copolymer concentration (10–100 wt%), the order can be gradually enhanced from short-range to long-range as proved by conventional techniques such as X-ray diffraction and electron microscopy. To evaluate the level of mesoscopic organization, the same series of samples is also analyzed by solid-state nuclear magnetic resonance (NMR) spectroscopy. The disorder-to-order transition is probed by 1H and 13C magic angle spinning NMR spectra through the increase in chemical environment uniformity and chain mobility respectively, which both result from the self-assembly mechanism. 1H NMR relaxation measurements (T 2) using low-field NMR spectroscopy are instrumental to identify the threshold template concentration where ordering takes place. [ABSTRACT FROM AUTHOR]