Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy
An extensive series of 128 halogen-bonded complexes formed by trimethylphosphine oxide and various F-, Cl-, Br-, I- and At-containing molecules, ranging in energy from 0 to 124 kJ/mol, is studied by DFT calculations in vacuum. The results reveal correlations between R−X⋅ͺ...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/6/1406 |
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| author | Alexei S. Ostras’ Daniil M. Ivanov Alexander S. Novikov Peter M. Tolstoy |
| author_facet | Alexei S. Ostras’ Daniil M. Ivanov Alexander S. Novikov Peter M. Tolstoy |
| author_sort | Alexei S. Ostras’ |
| collection | DOAJ |
| description | An extensive series of 128 halogen-bonded complexes formed by trimethylphosphine oxide and various F-, Cl-, Br-, I- and At-containing molecules, ranging in energy from 0 to 124 kJ/mol, is studied by DFT calculations in vacuum. The results reveal correlations between R−X⋅⋅⋅O=PMe<sub>3</sub> halogen bond energy Δ<i>E</i>, X⋅⋅⋅O distance <i>r</i>, halogen’s σ-hole size, QTAIM parameters at halogen bond critical point and changes of spectroscopic parameters of phosphine oxide upon complexation, such as <sup>31</sup>P NMR chemical shift, Δ<i>δ</i>P, and P=O stretching frequency, Δν. Some of the correlations are halogen-specific, i.e., different for F, Cl, Br, I and At, such as Δ<i>E</i>(<i>r</i>), while others are general, i.e., fulfilled for the whole set of complexes at once, such as Δ<i>E</i>(Δ<i>δ</i>P). The proposed correlations could be used to estimate the halogen bond properties in disordered media (liquids, solutions, polymers, glasses) from the corresponding NMR and IR spectra. |
| first_indexed | 2024-12-20T06:13:23Z |
| format | Article |
| id | doaj.art-da6c1a296808419cbc76e30aaff1566d |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T06:13:23Z |
| publishDate | 2020-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-da6c1a296808419cbc76e30aaff1566d2022-12-21T19:50:36ZengMDPI AGMolecules1420-30492020-03-01256140610.3390/molecules25061406molecules25061406Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation EnergyAlexei S. Ostras’0Daniil M. Ivanov1Alexander S. Novikov2Peter M. Tolstoy3Institute of Chemistry, St. Petersburg State University, 198504 St. Petersburg, RussiaInstitute of Chemistry, St. Petersburg State University, 198504 St. Petersburg, RussiaInstitute of Chemistry, St. Petersburg State University, 198504 St. Petersburg, RussiaInstitute of Chemistry, St. Petersburg State University, 198504 St. Petersburg, RussiaAn extensive series of 128 halogen-bonded complexes formed by trimethylphosphine oxide and various F-, Cl-, Br-, I- and At-containing molecules, ranging in energy from 0 to 124 kJ/mol, is studied by DFT calculations in vacuum. The results reveal correlations between R−X⋅⋅⋅O=PMe<sub>3</sub> halogen bond energy Δ<i>E</i>, X⋅⋅⋅O distance <i>r</i>, halogen’s σ-hole size, QTAIM parameters at halogen bond critical point and changes of spectroscopic parameters of phosphine oxide upon complexation, such as <sup>31</sup>P NMR chemical shift, Δ<i>δ</i>P, and P=O stretching frequency, Δν. Some of the correlations are halogen-specific, i.e., different for F, Cl, Br, I and At, such as Δ<i>E</i>(<i>r</i>), while others are general, i.e., fulfilled for the whole set of complexes at once, such as Δ<i>E</i>(Δ<i>δ</i>P). The proposed correlations could be used to estimate the halogen bond properties in disordered media (liquids, solutions, polymers, glasses) from the corresponding NMR and IR spectra.https://www.mdpi.com/1420-3049/25/6/1406halogen bondphosphine oxide<sup>31</sup>p nmr spectroscopyir spectroscopynon-covalent interactionsspectral correlations |
| spellingShingle | Alexei S. Ostras’ Daniil M. Ivanov Alexander S. Novikov Peter M. Tolstoy Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy Molecules halogen bond phosphine oxide <sup>31</sup>p nmr spectroscopy ir spectroscopy non-covalent interactions spectral correlations |
| title | Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy |
| title_full | Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy |
| title_fullStr | Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy |
| title_full_unstemmed | Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy |
| title_short | Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy |
| title_sort | phosphine oxides as spectroscopic halogen bond descriptors ir and nmr correlations with interatomic distances and complexation energy |
| topic | halogen bond phosphine oxide <sup>31</sup>p nmr spectroscopy ir spectroscopy non-covalent interactions spectral correlations |
| url | https://www.mdpi.com/1420-3049/25/6/1406 |
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