Direct cross-linking of silyl-functionalized cage siloxanes via nonhydrolytic siloxane bond formation for preparing nanoporous materials.

Bottom-up synthesis of siloxane-based nanoporous materials from siloxane oligomers is promising for constructing well-defined structures at a molecular level. Herein, we report the synthesis of nanoporous materials consisting of cage-type siloxanes through the nonhydrolytic siloxane bond formation reaction. Cage siloxanes with double- n -ring geometries ( n = 4 or 6) modified with dimethylsilyl and dimethylethoxysilyl groups are synthesized and directly cross-linked using a B(C ₆ F ₅ ) ₃ catalyst, resulting in the formation of porous networks composed of alternating cage siloxane nodes and tetramethyldisiloxane (-SiMe ₂ OSiMe ₂ -) linkers. Compared with conventional hydrolysis and polycondensation reactions of alkoxysilyl-modified cage siloxanes under acid conditions, the non-hydrolytic condensation reaction was found favorable for the formation of porous siloxane networks without unwanted cleavage of the siloxane bonds.