Functionalization of silica gel with organotrialkynyltins: new method of covalent attachment of organic groups on silica gel

Sandrine Boutet (1) , Bernard Jousseaume (1) , Thierry Toupance (1) , Monique Biesemans (2) , Rudolph Willem (2) , Christine Labrugère (3) , Laurent Delattre (4)

1 LCOO - Laboratoire de chimie organique et organométallique
2 High-Resolution NMR Centre
3 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux
4 SGR - Saint-Gobain Recherche

A new precursor molecule for chemical modification of oxide surfaces, the trialkynyl(fluoroorgano)tin(IV) (C4H9-CC)3Sn(CH2)2(CF2)7CF3, 1, was synthesized in three steps from tricyclohexyltin hydride. Compound 1 reacted with Biosepra 100 silica to give chain loadings as high as 0.28 mmol·g-1 to be compared to 0.44 mmol·g-1 reached with the trichlorosilane analogue Cl3Si(CH2)2(CF2)7CF3, 2. The modified powders have been thoroughly characterized using elemental analysis, FTIR spectroscopy, solid-state 29Si, 13C, and 29Si CP-MAS NMR, XPS, and TGA-MS. Irreversible chemisorption took place in solution at room temperature to give a fluorinated chain thin layer, likely a monolayer, via removal of three hex-1-yne molecules and formation of Sibulk-O-Sn-C linkages. The chemisorption process involves hydrolysis of the precursor in solution before reaction with the silica surface and led to surface-modified silica thermally stable up to 350 C. Trialkynylorganotins in solution might be therefore advantageously exploited to modify chemically SnO2 or TiO2 surfaces to get dye-sensitized oxide materials able to achieve light-to-electricity conversion.

Mots clés: Organic Groups; Organotrialkynyltins; Funtionalized; Covalent bond; Silica Gel

Domaines: Matériaux

Sandrine Boutet, Bernard Jousseaume, Thierry Toupance, Monique Biesemans, Rudolph Willem, et al.. Functionalization of silica gel with organotrialkynyltins: new method of covalent attachment of organic groups on silica gel. Chemistry of Materials, 2005, 17 (7), pp.1803-1811. ⟨10.1021/cm047886g⟩. ⟨hal-00085749⟩