Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State
A comprehensive study of saturated vapors of 4-n-propyloxybenzoic acid (POBA) by gas electron diffraction (GED) and mass spectrometric (MS) methods supplemented by quantum chemical (QC) calculations was carried out for the first time. An attempt was made to detect dimeric forms of the acid in the ga...
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MDPI AG
2022-12-01
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| Series: | International Journal of Molecular Sciences |
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| author | Nina I. Giricheva Ksenia E. Bubnova Alexander V. Krasnov Georgiy V. Girichev |
| author_facet | Nina I. Giricheva Ksenia E. Bubnova Alexander V. Krasnov Georgiy V. Girichev |
| author_sort | Nina I. Giricheva |
| collection | DOAJ |
| description | A comprehensive study of saturated vapors of 4-n-propyloxybenzoic acid (POBA) by gas electron diffraction (GED) and mass spectrometric (MS) methods supplemented by quantum chemical (QC) calculations was carried out for the first time. An attempt was made to detect dimeric forms of the acid in the gaseous state. It has been established that at the temperature of GED experiment, vapor over a solid sample contains up to 20 mol.% of cyclic dimers with two O-H...O hydrogen bonds. The main geometrical parameters of gaseous monomers and dimers of POBA are obtained. The distance r(O…O) = 2.574(12) Å in the cyclic fragment of the gaseous dimer is close to that in the crystal structure (2.611 Å). In the mass spectrum of the POBA recorded the ions of low intensity with a mass exceeding the molecular mass of the monomer were detected. The presence of ions, whose elemental composition corresponds to the dissociative ionization of the dimer, confirms the results of the GED experiment on the presence of POBA dimers in the gas state. The results of GED studies of acetic acid, benzoic acid, and POBA were compared. It is shown that the COOH fragment saves its geometric structure in monomers, as well as the COOH...HOOC fragment with two hydrogen bonds in dimers of different acids. The intermolecular interaction energy in considered acid dimers was estimated using QC calculations (B97D/6-311++G **). The significant value of last (>84 kJ/mol) is the reason for the noticeable presence of dimers in the gas phase. |
| first_indexed | 2024-03-09T17:45:07Z |
| format | Article |
| id | doaj.art-066ab3e76b7249acbe6c6525a8f95133 |
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| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T17:45:07Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-066ab3e76b7249acbe6c6525a8f951332023-11-24T11:12:59ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672022-12-0123231507910.3390/ijms232315079Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous StateNina I. Giricheva0Ksenia E. Bubnova1Alexander V. Krasnov2Georgiy V. Girichev3Nanomaterial Research Institute, Ivanovo State University, 153025 Ivanovo, RussiaDepartment of Physics, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, RussiaDepartment of Physics, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, RussiaDepartment of Physics, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, RussiaA comprehensive study of saturated vapors of 4-n-propyloxybenzoic acid (POBA) by gas electron diffraction (GED) and mass spectrometric (MS) methods supplemented by quantum chemical (QC) calculations was carried out for the first time. An attempt was made to detect dimeric forms of the acid in the gaseous state. It has been established that at the temperature of GED experiment, vapor over a solid sample contains up to 20 mol.% of cyclic dimers with two O-H...O hydrogen bonds. The main geometrical parameters of gaseous monomers and dimers of POBA are obtained. The distance r(O…O) = 2.574(12) Å in the cyclic fragment of the gaseous dimer is close to that in the crystal structure (2.611 Å). In the mass spectrum of the POBA recorded the ions of low intensity with a mass exceeding the molecular mass of the monomer were detected. The presence of ions, whose elemental composition corresponds to the dissociative ionization of the dimer, confirms the results of the GED experiment on the presence of POBA dimers in the gas state. The results of GED studies of acetic acid, benzoic acid, and POBA were compared. It is shown that the COOH fragment saves its geometric structure in monomers, as well as the COOH...HOOC fragment with two hydrogen bonds in dimers of different acids. The intermolecular interaction energy in considered acid dimers was estimated using QC calculations (B97D/6-311++G **). The significant value of last (>84 kJ/mol) is the reason for the noticeable presence of dimers in the gas phase.https://www.mdpi.com/1422-0067/23/23/150794-n-propyloxybenzoic acidhydrogen bonddimermolecular structuregas electron diffractionDFT |
| spellingShingle | Nina I. Giricheva Ksenia E. Bubnova Alexander V. Krasnov Georgiy V. Girichev Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State International Journal of Molecular Sciences 4-n-propyloxybenzoic acid hydrogen bond dimer molecular structure gas electron diffraction DFT |
| title | Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State |
| title_full | Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State |
| title_fullStr | Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State |
| title_full_unstemmed | Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State |
| title_short | Cyclic Dimers of 4-n-Propyloxybenzoic Acid with Hydrogen Bonds in the Gaseous State |
| title_sort | cyclic dimers of 4 n propyloxybenzoic acid with hydrogen bonds in the gaseous state |
| topic | 4-n-propyloxybenzoic acid hydrogen bond dimer molecular structure gas electron diffraction DFT |
| url | https://www.mdpi.com/1422-0067/23/23/15079 |
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