Hydrosilylation of Azide‐Containing Olefins as a Convenient Access to Azidoorganotrialkoxysilanes for Self‐Assembled Monolayer Elaboration onto Silica by Spin Coating

Abstract

We have developed a convenient and versatile synthetic methodology to prepare various azidoorganotrialkoxysilanes using the platinum‐catalyzed hydrosilylation of stable olefinic precursors with an azide function as the last step. Hydrosilylation of alkene‐functionalized aliphatic and aromatic azides featuring alkyl, urea, carbamate and pegylated moieties has been successfully achieved while preserving the integrity of the azide function. The spin coating technique has been used successfully to prepare one azide‐terminated monolayer in ambient atmosphere onto an oxide surface. This process has the advantages of being fast, simple, easy to handle and needs less solvent. The ability of the azide‐terminated surface to immobilize molecules via the copper‐catalyzed alkyne‐azide cycloaddition reaction has been demonstrated by Modulation Infrared Reflection‐Adsorption Spectroscopy using a probe molecule bearing a NO2 group.

Influence of the grafting process on the orientation and the reactivity of azide-terminated monolayers onto silica surface

“…Generally, commercially available organosilanes such as 11-azidoundecyltrimethoxysilane and p-azidomethylphenyltrimethoxysilane [37] were used to prepare azide-terminated SAMs. Recently, we have reported a versatile synthetic methodology to prepare various azidosilylated coupling agents using the platinum-catalyzed hydrosilylation of stable olefinic precursors bearing an azide group [38]. This new possibility opens the way to obtain new azide-terminated monolayers with modular composition and structure, leading to original physicochemical properties.…”

“…Only one example describes the deposition of an azide-terminated monolayer by the Langmuir-Blodgett technique [45]. Recently, we have successfully prepared an azide-terminated SAM by using the spin coating technique in ambient atmosphere [38]. This is an interesting alternative process that is fast, simple, easy to handle and requires less solvent.…”

Stack‐and‐Draw Applied to the Engineering of Multi‐Material Fibers with Non‐Cylindrical Profiles

“…The optical fibers were immersed in a silanization flask under an inert atmosphere (N 2 ) and exposed for 16 h to a solution containing 11‐bromoundecyltrimethoxysilane (5 × 10 −5 mol) synthesized according to literature and trichloroacetic acid (TCA, 5 × 10 −6 mol) in 200 mL of anhydrous toluene at 20 °C. [ 30 ] The fibers were then rinsed by multiple cycles of 5 min sonication in toluene, water, and chloroform (twice per solvent) and dried under nitrogen flow. The bromide moieties of the SAM were then replaced via nucleophilic substitution with azide by immersing the fibers in a saturated solution of NaN 3 on anhydrous DMF for 48 h at room temperature under an inert atmosphere.…”

“…Then, this SAM-Br undergoes a modification of the terminal bromine substituted by an azide. [30,31] The resulted azide-terminated SAM constitutes a universal reactive molecular platform to Table 1. Physical properties of the materials involved in the present work: Refractive index measured at 589 nm (n@ 589nm ), glass transition temperature (T g ), drawing temperature range (T Draw ), melting temperature (T m ), density (d), and electric resistivity (ρ).…”

“…Then, this SAM‐Br undergoes a modification of the terminal bromine substituted by an azide. [ 30, 31 ] The resulted azide‐terminated SAM constitutes a universal reactive molecular platform to immobilize covalently (bio)molecular probe by an azide–alkyne click chemistry [ 32,33 ] (See “Experimental” section for the full description of the fiber surface preparation mechanism).…”