Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane
The tautomerism in the title compound as a potential long-range proton transfer (PT) switch has been studied by using the DFT and TD-DFT approaches. The data show that in aprotic solvents, the enol tautomer dominates, while the increase in the content of the keto tautomer (short-range PT) rises as a...
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| Format: | Article |
| Language: | English |
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MDPI AG
2024-03-01
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| Series: | Physchem |
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| Online Access: | https://www.mdpi.com/2673-7167/4/1/7 |
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| author | Daniela Nedeltcheva-Antonova Liudmil Antonov |
| author_facet | Daniela Nedeltcheva-Antonova Liudmil Antonov |
| author_sort | Daniela Nedeltcheva-Antonova |
| collection | DOAJ |
| description | The tautomerism in the title compound as a potential long-range proton transfer (PT) switch has been studied by using the DFT and TD-DFT approaches. The data show that in aprotic solvents, the enol tautomer dominates, while the increase in the content of the keto tautomer (short-range PT) rises as a function of polarity of the solvent. In ethanol, due to specific solute–solvent stabilization through intermolecular hydrogen bonding, a substantial amount of the keto forms exists in solution. The irradiation leads to two competitive processes in the excited state, namely ESIPT and trans/cis isomerization around the azomethine bond as in other structurally similar Schiff bases. The studied compound is not suitable for bistable tautomeric switching, where long-range PT occurs, due to the difficult enolization of the coumarin carbonyl group. |
| first_indexed | 2024-04-24T17:54:26Z |
| format | Article |
| id | doaj.art-553117ddbde3422ea8f78740bbe44921 |
| institution | Directory Open Access Journal |
| issn | 2673-7167 |
| language | English |
| last_indexed | 2024-04-24T17:54:26Z |
| publishDate | 2024-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Physchem |
| spelling | doaj.art-553117ddbde3422ea8f78740bbe449212024-03-27T14:00:21ZengMDPI AGPhyschem2673-71672024-03-01419110510.3390/physchem4010007Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton CraneDaniela Nedeltcheva-Antonova0Liudmil Antonov1Institute of Electronics, Bulgarian Academy of Sciences, 1784 Sofia, BulgariaInstitute of Electronics, Bulgarian Academy of Sciences, 1784 Sofia, BulgariaThe tautomerism in the title compound as a potential long-range proton transfer (PT) switch has been studied by using the DFT and TD-DFT approaches. The data show that in aprotic solvents, the enol tautomer dominates, while the increase in the content of the keto tautomer (short-range PT) rises as a function of polarity of the solvent. In ethanol, due to specific solute–solvent stabilization through intermolecular hydrogen bonding, a substantial amount of the keto forms exists in solution. The irradiation leads to two competitive processes in the excited state, namely ESIPT and trans/cis isomerization around the azomethine bond as in other structurally similar Schiff bases. The studied compound is not suitable for bistable tautomeric switching, where long-range PT occurs, due to the difficult enolization of the coumarin carbonyl group.https://www.mdpi.com/2673-7167/4/1/77-hydroxy-coumarin7-hydroxy-3-methylcoumarinSchiff basetautomerismDFTTD-DFT |
| spellingShingle | Daniela Nedeltcheva-Antonova Liudmil Antonov Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane Physchem 7-hydroxy-coumarin 7-hydroxy-3-methylcoumarin Schiff base tautomerism DFT TD-DFT |
| title | Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane |
| title_full | Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane |
| title_fullStr | Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane |
| title_full_unstemmed | Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane |
| title_short | Ground-State Tautomerism and Excited-State Proton Transfer in 7-Hydroxy-4-methyl-8-((phenylimino)methyl)-2H-chromen-2-one as a Potential Proton Crane |
| title_sort | ground state tautomerism and excited state proton transfer in 7 hydroxy 4 methyl 8 phenylimino methyl 2h chromen 2 one as a potential proton crane |
| topic | 7-hydroxy-coumarin 7-hydroxy-3-methylcoumarin Schiff base tautomerism DFT TD-DFT |
| url | https://www.mdpi.com/2673-7167/4/1/7 |
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