Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers
Jelle Jamoul,
Sambhu Radhakrishnan,
Maarten Houlleberghs,
C. Vinod Chandran,
Aline Vits,
Pasquinel Weckx,
Sam Smet,
Daniel Arenas Esteban,
Sara Bals,
Johan A. Martens,
Eric Breynaert
Affiliations
Jelle Jamoul
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Sambhu Radhakrishnan
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Maarten Houlleberghs
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
C. Vinod Chandran
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Aline Vits
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Pasquinel Weckx
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Sam Smet
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Daniel Arenas Esteban
Electron Microscopy for Materials Science (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium
Sara Bals
Electron Microscopy for Materials Science (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium
Johan A. Martens
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
Eric Breynaert
Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
This work describes the synthesis of ordered 3D siloxane-silsesquioxane reticular materials with silicate D4R cubes (Si8O208−), harvested from a sacrificial tetrabutylammonium cyclosilicate hydrate (TBA-CySH) precursor, interlinked with octyl and dicyclopentyl (Cp2) hydrocarbon functionalities in a one-step synthesis with organodichlorosilanes. Advanced solid-state NMR spectroscopy allowed us to unravel the molecular order of the nodes and their interconnection by the silicone linkers. In the case of octyl-methyl silicone linkers, changing the silane-to-silicate ratio in the synthesis allowed for tuning the length of the linker between the nodes. With dicyclopentyl linkers, the addition of dimethyldichlorosilane was essential to enable the formation of a reticular network. The resulting materials contained mixed, dimeric silicone linkers, i.e., Si8-O-Si(Me2)-O-Si(Cp2)-O-Si8.
