Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation
The photodegradation mechanism of 1-phenyl-4-allyl-tetrazol-5-one has been studied using (time-dependent) density functional theory with the M06-HF, B3LYP, and PBE0 functionals and the VDZ basis set. All calculations have been carried out using the polarizable continuum model to simulate the solvent...
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MDPI AG
2021-04-01
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| Online Access: | https://www.mdpi.com/2076-3417/11/9/4045 |
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| author | Amilcar Duque-Prata Carlos Serpa Pedro J. S. B. Caridade |
| author_facet | Amilcar Duque-Prata Carlos Serpa Pedro J. S. B. Caridade |
| author_sort | Amilcar Duque-Prata |
| collection | DOAJ |
| description | The photodegradation mechanism of 1-phenyl-4-allyl-tetrazol-5-one has been studied using (time-dependent) density functional theory with the M06-HF, B3LYP, and PBE0 functionals and the VDZ basis set. All calculations have been carried out using the polarizable continuum model to simulate the solvent effects of methanol. The reaction pathway evolution on the triplet state has been characterised to validate a previously postulated experimental-based mechanism. The transition states and minimums have been initially located by local scanning in partial constrained optimisation, followed by a fully relaxed search procedure. The UV spectra has shown to be better described with PBE0 functional when compared with the experimental results, having the M06-HF a shift of 40 nm. From the energetic point of view, the postulated mechanism has been validated in this work showing a concerted photoextrusion of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi mathvariant="normal">N</mi><mn>2</mn></msub></semantics></math></inline-formula> molecule. The intramolecular proton transfer occurs at a later stage of the mechanism after cyclization of the allyl group on a triplet biradical intermediate. The photoproduct observed experimentally, a pyrimidinone, has been characterised. The infrared spectroscopic reaction profile has also been proposed. |
| first_indexed | 2024-03-10T11:51:08Z |
| format | Article |
| id | doaj.art-6d1edd1a5648493d85d030513d5ab7c5 |
| institution | Directory Open Access Journal |
| issn | 2076-3417 |
| language | English |
| last_indexed | 2024-03-10T11:51:08Z |
| publishDate | 2021-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Applied Sciences |
| spelling | doaj.art-6d1edd1a5648493d85d030513d5ab7c52023-11-21T17:43:39ZengMDPI AGApplied Sciences2076-34172021-04-01119404510.3390/app11094045Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism ElucidationAmilcar Duque-Prata0Carlos Serpa1Pedro J. S. B. Caridade2Department of Chemistry, University of Coimbra, CQC Rua Larga, 3004-545 Coimbra, PortugalDepartment of Chemistry, University of Coimbra, CQC Rua Larga, 3004-545 Coimbra, PortugalDepartment of Chemistry, University of Coimbra, CQC Rua Larga, 3004-545 Coimbra, PortugalThe photodegradation mechanism of 1-phenyl-4-allyl-tetrazol-5-one has been studied using (time-dependent) density functional theory with the M06-HF, B3LYP, and PBE0 functionals and the VDZ basis set. All calculations have been carried out using the polarizable continuum model to simulate the solvent effects of methanol. The reaction pathway evolution on the triplet state has been characterised to validate a previously postulated experimental-based mechanism. The transition states and minimums have been initially located by local scanning in partial constrained optimisation, followed by a fully relaxed search procedure. The UV spectra has shown to be better described with PBE0 functional when compared with the experimental results, having the M06-HF a shift of 40 nm. From the energetic point of view, the postulated mechanism has been validated in this work showing a concerted photoextrusion of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi mathvariant="normal">N</mi><mn>2</mn></msub></semantics></math></inline-formula> molecule. The intramolecular proton transfer occurs at a later stage of the mechanism after cyclization of the allyl group on a triplet biradical intermediate. The photoproduct observed experimentally, a pyrimidinone, has been characterised. The infrared spectroscopic reaction profile has also been proposed.https://www.mdpi.com/2076-3417/11/9/4045density functional theoryphotochemistrytetrazolesreaction pathwaytriplet state |
| spellingShingle | Amilcar Duque-Prata Carlos Serpa Pedro J. S. B. Caridade Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation Applied Sciences density functional theory photochemistry tetrazoles reaction pathway triplet state |
| title | Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation |
| title_full | Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation |
| title_fullStr | Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation |
| title_full_unstemmed | Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation |
| title_short | Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation |
| title_sort | photochemistry of 1 phenyl 4 allyl tetrazol 5 one a theoretical study contribution towards mechanism elucidation |
| topic | density functional theory photochemistry tetrazoles reaction pathway triplet state |
| url | https://www.mdpi.com/2076-3417/11/9/4045 |
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