Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers
This work describes the synthesis of ordered 3D siloxane-silsesquioxane reticular materials with silicate D4R cubes (Si<sub>8</sub>O<sub>20</sub><sup>8−</sup>), harvested from a sacrificial tetrabutylammonium cyclosilicate hydrate (TBA-CySH) precursor, interlinked...
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2025-01-01
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| Online Access: | https://www.mdpi.com/1420-3049/30/2/228 |
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| author | 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 |
| author_facet | 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 |
| author_sort | Jelle Jamoul |
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| description | This work describes the synthesis of ordered 3D siloxane-silsesquioxane reticular materials with silicate D4R cubes (Si<sub>8</sub>O<sub>20</sub><sup>8−</sup>), harvested from a sacrificial tetrabutylammonium cyclosilicate hydrate (TBA-CySH) precursor, interlinked with octyl and dicyclopentyl (Cp<sub>2</sub>) 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., Si<sub>8</sub>-O-Si(Me<sub>2</sub>)-O-Si(Cp<sub>2</sub>)-O-Si<sub>8</sub>. |
| format | Article |
| id | doaj-art-bd69bc7a35894c03b15b9c542119ab4f |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-bd69bc7a35894c03b15b9c542119ab4f2025-01-24T13:43:11ZengMDPI AGMolecules1420-30492025-01-0130222810.3390/molecules30020228Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone LinkersJelle Jamoul0Sambhu Radhakrishnan1Maarten Houlleberghs2C. Vinod Chandran3Aline Vits4Pasquinel Weckx5Sam Smet6Daniel Arenas Esteban7Sara Bals8Johan A. Martens9Eric Breynaert10Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumElectron Microscopy for Materials Science (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, BelgiumElectron Microscopy for Materials Science (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumCentre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT), KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, BelgiumThis work describes the synthesis of ordered 3D siloxane-silsesquioxane reticular materials with silicate D4R cubes (Si<sub>8</sub>O<sub>20</sub><sup>8−</sup>), harvested from a sacrificial tetrabutylammonium cyclosilicate hydrate (TBA-CySH) precursor, interlinked with octyl and dicyclopentyl (Cp<sub>2</sub>) 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., Si<sub>8</sub>-O-Si(Me<sub>2</sub>)-O-Si(Cp<sub>2</sub>)-O-Si<sub>8</sub>.https://www.mdpi.com/1420-3049/30/2/228reticular material synthesissilicate-silicone hybridsPOSiSilscyclosilicate hydratesiloxane-silsesquioxaneoctyl-methyldichlorosilane |
| spellingShingle | 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 Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers Molecules reticular material synthesis silicate-silicone hybrids POSiSils cyclosilicate hydrate siloxane-silsesquioxane octyl-methyldichlorosilane |
| title | Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers |
| title_full | Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers |
| title_fullStr | Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers |
| title_full_unstemmed | Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers |
| title_short | Synthesis and Advanced NMR Characterization of Ordered 3D Reticular Materials with PolySilicate Nodes and Hydrophobic OrganoSilicone Linkers |
| title_sort | synthesis and advanced nmr characterization of ordered 3d reticular materials with polysilicate nodes and hydrophobic organosilicone linkers |
| topic | reticular material synthesis silicate-silicone hybrids POSiSils cyclosilicate hydrate siloxane-silsesquioxane octyl-methyldichlorosilane |
| url | https://www.mdpi.com/1420-3049/30/2/228 |
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