A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study
The formation of a halogen-bonded network using four NHX-(CH<sub>2</sub>)<sub>3</sub>-NX-(CH<sub>2</sub>)<sub>3</sub>-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structur...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-12-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/12/1/16 |
| _version_ | 1797343421433643008 |
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| author | Rubén D. Parra |
| author_facet | Rubén D. Parra |
| author_sort | Rubén D. Parra |
| collection | DOAJ |
| description | The formation of a halogen-bonded network using four NHX-(CH<sub>2</sub>)<sub>3</sub>-NX-(CH<sub>2</sub>)<sub>3</sub>-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C<sub>4h</sub> symmetry, with one halogen-bonded network located at each end of the structure and one at its center. Each halogen-bonded network has four quasi-planar N-X···N interactions with binding energies that increase with the size of X. The structure is found to bind Li<sup>+</sup> at each of the halogen-bonded networks, albeit more strongly at its center. The binding of Li<sup>+</sup> is driven by halogen atom lone pairs that produce a rich electron density orthogonal to the halogen bond. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, IRC calculations are performed to examine the transitions between the Li<sup>+</sup> complex minima and, thus, the potential for transporting the metal ion from one end of the tube to the other. Based on the tetrameric structure, a model intramolecular structure is built and considered as a potential host for Li<sup>+</sup>. In this case, the central intermolecular N-X···N network is replaced by an intramolecular Si-C≡C-Si network. Interestingly, both intermolecular and intramolecular structures exhibit similar Li<sup>+</sup> binding abilities. |
| first_indexed | 2024-03-08T10:47:19Z |
| format | Article |
| id | doaj.art-89e7964141ae46c69d053124b0f88a17 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-08T10:47:19Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-89e7964141ae46c69d053124b0f88a172024-01-26T17:04:00ZengMDPI AGInorganics2304-67402023-12-011211610.3390/inorganics12010016A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT StudyRubén D. Parra0Department of Chemistry and Biochemistry, DePaul University, Chicago, IL 60614, USAThe formation of a halogen-bonded network using four NHX-(CH<sub>2</sub>)<sub>3</sub>-NX-(CH<sub>2</sub>)<sub>3</sub>-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C<sub>4h</sub> symmetry, with one halogen-bonded network located at each end of the structure and one at its center. Each halogen-bonded network has four quasi-planar N-X···N interactions with binding energies that increase with the size of X. The structure is found to bind Li<sup>+</sup> at each of the halogen-bonded networks, albeit more strongly at its center. The binding of Li<sup>+</sup> is driven by halogen atom lone pairs that produce a rich electron density orthogonal to the halogen bond. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, IRC calculations are performed to examine the transitions between the Li<sup>+</sup> complex minima and, thus, the potential for transporting the metal ion from one end of the tube to the other. Based on the tetrameric structure, a model intramolecular structure is built and considered as a potential host for Li<sup>+</sup>. In this case, the central intermolecular N-X···N network is replaced by an intramolecular Si-C≡C-Si network. Interestingly, both intermolecular and intramolecular structures exhibit similar Li<sup>+</sup> binding abilities.https://www.mdpi.com/2304-6740/12/1/16halogen bondhalogen-bonded intermolecular networkLi<sup>+</sup> binding and transportmetal ion binding and transportmetal ion channelDFT |
| spellingShingle | Rubén D. Parra A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study Inorganics halogen bond halogen-bonded intermolecular network Li<sup>+</sup> binding and transport metal ion binding and transport metal ion channel DFT |
| title | A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study |
| title_full | A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study |
| title_fullStr | A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study |
| title_full_unstemmed | A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study |
| title_short | A Model Halogen-Bonded Network as a Potential Tube-like Host for Li<sup>+</sup>: A DFT Study |
| title_sort | model halogen bonded network as a potential tube like host for li sup sup a dft study |
| topic | halogen bond halogen-bonded intermolecular network Li<sup>+</sup> binding and transport metal ion binding and transport metal ion channel DFT |
| url | https://www.mdpi.com/2304-6740/12/1/16 |
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