Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis
The peculiarities of the optical properties of 2-aryl-1,2,3-triazole acids and their sodium salts were investigated in different solvents (1,4-dioxane, dimethyl sulfoxide DMSO, methanol MeOH) and in mixtures with water. The results were discussed in terms of the molecular structure formed by inter-...
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MDPI AG
2023-05-01
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| Series: | International Journal of Molecular Sciences |
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| author | Nikita E. Safronov Irena P. Kostova Mauricio Alcolea Palafox Nataliya P. Belskaya |
| author_facet | Nikita E. Safronov Irena P. Kostova Mauricio Alcolea Palafox Nataliya P. Belskaya |
| author_sort | Nikita E. Safronov |
| collection | DOAJ |
| description | The peculiarities of the optical properties of 2-aryl-1,2,3-triazole acids and their sodium salts were investigated in different solvents (1,4-dioxane, dimethyl sulfoxide DMSO, methanol MeOH) and in mixtures with water. The results were discussed in terms of the molecular structure formed by inter- and intramolecular noncovalent interactions (NCIs) and their ability to ionize in anions. Theoretical calculations using the Time-Dependent Density Functional Theory (TDDFT) were carried out in different solvents to support the results. In polar and nonpolar solvents (DMSO, 1,4-dioxane), fluorescence was provided by strong neutral associates. Protic MeOH can weaken the acid molecules’ association, forming other fluorescent species. The fluorescent species in water exhibited similar optical characteristics to those of triazole salts; therefore, their anionic character can be assumed. Experimental <sup>1</sup>H and <sup>13</sup>C-NMR spectra were compared to their corresponding calculated spectra using the Gauge-Independent Atomic Orbital (GIAO) method and several relationships were established. All these findings showed that the obtained photophysical properties of the 2-aryl-1,2,3-triazole acids noticeably depend on the environment and, therefore, are good candidates as sensors for the identification of analytes with labile protons. |
| first_indexed | 2024-03-11T03:39:11Z |
| format | Article |
| id | doaj.art-07c5af6e4bc2476b90ca16678d8a3b6f |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T03:39:11Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-07c5af6e4bc2476b90ca16678d8a3b6f2023-11-18T01:44:43ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-05-012410894710.3390/ijms24108947Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures AnalysisNikita E. Safronov0Irena P. Kostova1Mauricio Alcolea Palafox2Nataliya P. Belskaya3Department of Technology for Organic Synthesis, Ural Federal University, 19 Mira Str., Yekaterinburg 620002, RussiaDepartment of Chemistry, Faculty of Pharmacy, Medical University—Sofia, 2 Dunav Str., 1000 Sofia, BulgariaDepartamento de Química Física, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, SpainDepartment of Technology for Organic Synthesis, Ural Federal University, 19 Mira Str., Yekaterinburg 620002, RussiaThe peculiarities of the optical properties of 2-aryl-1,2,3-triazole acids and their sodium salts were investigated in different solvents (1,4-dioxane, dimethyl sulfoxide DMSO, methanol MeOH) and in mixtures with water. The results were discussed in terms of the molecular structure formed by inter- and intramolecular noncovalent interactions (NCIs) and their ability to ionize in anions. Theoretical calculations using the Time-Dependent Density Functional Theory (TDDFT) were carried out in different solvents to support the results. In polar and nonpolar solvents (DMSO, 1,4-dioxane), fluorescence was provided by strong neutral associates. Protic MeOH can weaken the acid molecules’ association, forming other fluorescent species. The fluorescent species in water exhibited similar optical characteristics to those of triazole salts; therefore, their anionic character can be assumed. Experimental <sup>1</sup>H and <sup>13</sup>C-NMR spectra were compared to their corresponding calculated spectra using the Gauge-Independent Atomic Orbital (GIAO) method and several relationships were established. All these findings showed that the obtained photophysical properties of the 2-aryl-1,2,3-triazole acids noticeably depend on the environment and, therefore, are good candidates as sensors for the identification of analytes with labile protons.https://www.mdpi.com/1422-0067/24/10/89471,2,3-triazolescarboxylic acidfluorescenceTDDFTdimerp<i>K</i><sub>a</sub> |
| spellingShingle | Nikita E. Safronov Irena P. Kostova Mauricio Alcolea Palafox Nataliya P. Belskaya Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis International Journal of Molecular Sciences 1,2,3-triazoles carboxylic acid fluorescence TDDFT dimer p<i>K</i><sub>a</sub> |
| title | Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis |
| title_full | Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis |
| title_fullStr | Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis |
| title_full_unstemmed | Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis |
| title_short | Combined NMR Spectroscopy and Quantum-Chemical Calculations in Fluorescent 1,2,3-Triazole-4-carboxylic Acids Fine Structures Analysis |
| title_sort | combined nmr spectroscopy and quantum chemical calculations in fluorescent 1 2 3 triazole 4 carboxylic acids fine structures analysis |
| topic | 1,2,3-triazoles carboxylic acid fluorescence TDDFT dimer p<i>K</i><sub>a</sub> |
| url | https://www.mdpi.com/1422-0067/24/10/8947 |
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