Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes
The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. S...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | en_US |
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John Wiley & Sons, Inc
2014
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| Online Access: | http://hdl.handle.net/1721.1/87685 https://orcid.org/0000-0003-1589-832X https://orcid.org/0000-0002-6708-7660 https://orcid.org/0000-0001-7045-1200 |
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| author | Li, Xiansen Michaelis, Vladimir K. Ong, Ta-Chung Smith, Stacey J. Griffin, Robert Guy Wang, Evelyn |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Li, Xiansen Michaelis, Vladimir K. Ong, Ta-Chung Smith, Stacey J. Griffin, Robert Guy Wang, Evelyn |
| author_sort | Li, Xiansen |
| collection | MIT |
| description | The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+[BOND]O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal–organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. |
| first_indexed | 2024-09-23T08:04:14Z |
| format | Article |
| id | mit-1721.1/87685 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:04:14Z |
| publishDate | 2014 |
| publisher | John Wiley & Sons, Inc |
| record_format | dspace |
| spelling | mit-1721.1/876852022-09-23T10:38:53Z Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes Li, Xiansen Michaelis, Vladimir K. Ong, Ta-Chung Smith, Stacey J. Griffin, Robert Guy Wang, Evelyn Massachusetts Institute of Technology. Department of Chemistry Massachusetts Institute of Technology. Department of Mechanical Engineering Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology) Li, Xiansen Li, Xiansen Wang, Evelyn N. Michaelis, Vladimir K. Ong, Ta-Chung Griffin, Robert Guy Smith, Stacey J. The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+[BOND]O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal–organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. United States. Defense Advanced Research Projects Agency (control No. 0471-1627) National Institute for Biomedical Imaging and Bioengineering (U.S.) (award No. EB-001960) National Institutes of Health (U.S.) (NIBIB award No. EB-002026) National Science Foundation (U.S.) (Grant No. CHE-0946721) 2014-06-06T17:08:26Z 2014-06-06T17:08:26Z 2014-05 Article http://purl.org/eprint/type/JournalArticle 09476539 http://hdl.handle.net/1721.1/87685 Li, Xiansen, Vladimir K. Michaelis, Ta-Chung Ong, Stacey J. Smith, Robert G. Griffin, and Evelyn N. Wang. “Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-Coordinate Silicon Alcoholate Complexes.” Chem. Eur. J. 20, no. 21 (May 19, 2014): 6315–6323. https://orcid.org/0000-0003-1589-832X https://orcid.org/0000-0002-6708-7660 https://orcid.org/0000-0001-7045-1200 en_US http://dx.doi.org/10.1002/chem.201400379 Chemistry - A European Journal Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf John Wiley & Sons, Inc Li |
| spellingShingle | Li, Xiansen Michaelis, Vladimir K. Ong, Ta-Chung Smith, Stacey J. Griffin, Robert Guy Wang, Evelyn Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes |
| title | Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes |
| title_full | Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes |
| title_fullStr | Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes |
| title_full_unstemmed | Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes |
| title_short | Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes |
| title_sort | designed single step synthesis structure and derivative textural properties of well ordered layered penta coordinate silicon alcoholate complexes |
| url | http://hdl.handle.net/1721.1/87685 https://orcid.org/0000-0003-1589-832X https://orcid.org/0000-0002-6708-7660 https://orcid.org/0000-0001-7045-1200 |
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