Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds
Ester hydrates, as the intermediates of the esterification between acid and alcohol, are very short-lived and challenging to be trapped. Therefore, the crystal structures of ester hydrates have rarely been characterized. Herein, we present that the mono-deprotonated ester hydrates [CH<sub>3<...
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MDPI AG
2023-07-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/15/5705 |
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| author | Bin Wang Zi-Ang Nan Qing Li Jin Liu Zi-Xiu Lu Wei Wang Zhu Zhuo Guo-Ling Li You-Gui Huang |
| author_facet | Bin Wang Zi-Ang Nan Qing Li Jin Liu Zi-Xiu Lu Wei Wang Zhu Zhuo Guo-Ling Li You-Gui Huang |
| author_sort | Bin Wang |
| collection | DOAJ |
| description | Ester hydrates, as the intermediates of the esterification between acid and alcohol, are very short-lived and challenging to be trapped. Therefore, the crystal structures of ester hydrates have rarely been characterized. Herein, we present that the mono-deprotonated ester hydrates [CH<sub>3</sub>OSO<sub>2</sub>(OH)<sub>2</sub>]<sup>−</sup>, serving as the template for the self-assembly of a π-stacked boat-shaped macrocycle (CH<sub>3</sub>OSO<sub>2</sub>(OH)<sub>2</sub>)<sub>0.67</sub>(CH<sub>3</sub>OSO<sub>3</sub>)<sub>1.33</sub>@{[ClLCo<sup>II</sup>]<sub>6</sub>}·Cl<sub>4</sub>·13CH<sub>3</sub>OH·9H<sub>2</sub>O (<b>1</b>) (L = tris(2-benzimidazolylmethyl) amine), can be trapped in the host by multiple NH···O hydrogen bonds. In the solution of CoCl<sub>2</sub>, L, and H<sub>2</sub>SO<sub>4</sub> in MeOH, HSO<sub>4</sub><sup>−</sup> reacts with MeOH, producing [CH<sub>3</sub>OSO<sub>3</sub>]<sup>−</sup> via the ester hydrate intermediate of [CH<sub>3</sub>OSO<sub>3</sub>(OH)<sub>2</sub>]<sup>−</sup>. Both the product and the intermediate serve as the template directing the self-assembly of the π-stacked macrocycle, in which the short-lived ester hydrate is firmly trapped and stabilized, as revealed by single-crystal analysis. |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T00:21:50Z |
| publishDate | 2023-07-01 |
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| series | Molecules |
| spelling | doaj.art-b62ac440375349f6984b0b3cbc59ec602023-11-18T23:17:47ZengMDPI AGMolecules1420-30492023-07-012815570510.3390/molecules28155705Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen BondsBin Wang0Zi-Ang Nan1Qing Li2Jin Liu3Zi-Xiu Lu4Wei Wang5Zhu Zhuo6Guo-Ling Li7You-Gui Huang8CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaEster hydrates, as the intermediates of the esterification between acid and alcohol, are very short-lived and challenging to be trapped. Therefore, the crystal structures of ester hydrates have rarely been characterized. Herein, we present that the mono-deprotonated ester hydrates [CH<sub>3</sub>OSO<sub>2</sub>(OH)<sub>2</sub>]<sup>−</sup>, serving as the template for the self-assembly of a π-stacked boat-shaped macrocycle (CH<sub>3</sub>OSO<sub>2</sub>(OH)<sub>2</sub>)<sub>0.67</sub>(CH<sub>3</sub>OSO<sub>3</sub>)<sub>1.33</sub>@{[ClLCo<sup>II</sup>]<sub>6</sub>}·Cl<sub>4</sub>·13CH<sub>3</sub>OH·9H<sub>2</sub>O (<b>1</b>) (L = tris(2-benzimidazolylmethyl) amine), can be trapped in the host by multiple NH···O hydrogen bonds. In the solution of CoCl<sub>2</sub>, L, and H<sub>2</sub>SO<sub>4</sub> in MeOH, HSO<sub>4</sub><sup>−</sup> reacts with MeOH, producing [CH<sub>3</sub>OSO<sub>3</sub>]<sup>−</sup> via the ester hydrate intermediate of [CH<sub>3</sub>OSO<sub>3</sub>(OH)<sub>2</sub>]<sup>−</sup>. Both the product and the intermediate serve as the template directing the self-assembly of the π-stacked macrocycle, in which the short-lived ester hydrate is firmly trapped and stabilized, as revealed by single-crystal analysis.https://www.mdpi.com/1420-3049/28/15/5705ester hydrateself-assemblyπ-stacking interactionhydrogen bondingintermediate |
| spellingShingle | Bin Wang Zi-Ang Nan Qing Li Jin Liu Zi-Xiu Lu Wei Wang Zhu Zhuo Guo-Ling Li You-Gui Huang Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds Molecules ester hydrate self-assembly π-stacking interaction hydrogen bonding intermediate |
| title | Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds |
| title_full | Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds |
| title_fullStr | Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds |
| title_full_unstemmed | Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds |
| title_short | Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds |
| title_sort | trapping an ester hydrate intermediate in a π stacked macrocycle with multiple hydrogen bonds |
| topic | ester hydrate self-assembly π-stacking interaction hydrogen bonding intermediate |
| url | https://www.mdpi.com/1420-3049/28/15/5705 |
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