A general method for preparing bridged organosilanes with pendant functional groups and functional mesoporous organosilicas.

Abstract

New organosilica precursors containing two triethoxysilyl groups suitable for the organosilica material formation through the sol-gel process were designed and synthesised. These precursors display alkyne or azide groups for attaching targeted functional groups by copper-catalysed azide-alkyne cycloaddition (CuAAC) and can be used for the preparation of functional organosilicas following two strategies: 1) the functional group is first appended by CuAAC under anhydrous conditions, then the functional material is prepared by the sol-gel process; 2) the precursor is first subjected to the sol-gel process, producing porous, clickable bridged silsesquioxanes or periodic mesoporous organosilicas (PMOs), then the desired functional groups are attached by means of CuAAC. Herein, we show the feasibility of both approaches. A series of bridged bis(triethoxysilane)s with different pending organic moieties was prepared, demonstrating the compatibility of the first approach with many functional groups. In particular, we demonstrate that organic functional molecules bearing only one derivatisation site can be used to produce bridged organosilanes and bridged silsesquioxanes. In the second approach, clickable PMOs and porous bridged silsesquioxanes were prepared from the alkyne- or azide-containing precursors, and thereafter, functionalised with complementary model azide- or alkyne-containing molecules. These results confirmed the potential of this approach as a general methodology for preparing functional organosilicas with high loadings of functional groups. Both approaches give rise to a wide range of new functional organosilica materials.