{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,22]],"date-time":"2026-01-22T14:58:13Z","timestamp":1769093893533,"version":"3.49.0"},"reference-count":52,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2021,4,29]],"date-time":"2021-04-29T00:00:00Z","timestamp":1619654400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/00313\/2020"],"award-info":[{"award-number":["UIDB\/00313\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Applied Sciences"],"abstract":"<jats:p>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 N2 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.<\/jats:p>","DOI":"10.3390\/app11094045","type":"journal-article","created":{"date-parts":[[2021,4,29]],"date-time":"2021-04-29T04:30:11Z","timestamp":1619670611000},"page":"4045","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Photochemistry of 1-Phenyl-4-Allyl-Tetrazol-5-One: A Theoretical Study Contribution towards Mechanism Elucidation"],"prefix":"10.3390","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0512-3443","authenticated-orcid":false,"given":"Amilcar","family":"Duque-Prata","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Coimbra, CQC Rua Larga, 3004-545 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7004-0110","authenticated-orcid":false,"given":"Carlos","family":"Serpa","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Coimbra, CQC Rua Larga, 3004-545 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0947-5750","authenticated-orcid":false,"given":"Pedro J. S. B.","family":"Caridade","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Coimbra, CQC Rua Larga, 3004-545 Coimbra, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2021,4,29]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1007\/s10593-007-0001-5","article-title":"Drugs in the tetrazole series. Review","volume":"43","author":"Myznikov","year":"2007","journal-title":"Chem. Heterocycl. Compd."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"84","DOI":"10.1039\/B616738C","article-title":"In situ hydrothermal synthesis of tetrazole coordination polymers with interesting physical properties","volume":"37","author":"Zhao","year":"2008","journal-title":"Chem. Soc. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3009","DOI":"10.1002\/chem.201504520","article-title":"\u03b1-Amino Acid-Isosteric \u03b1-Amino Tetrazoles","volume":"22","author":"Zhao","year":"2016","journal-title":"Chem. Eur. J."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2410","DOI":"10.1016\/j.bmc.2009.02.004","article-title":"Azole antimicrobial pharmacophore-based tetrazoles: Synthesis and biological evaluation as potential antimicrobial and anticonvulsant agents","volume":"17","author":"Rostom","year":"2009","journal-title":"Bioorganic Med. Chem."},{"key":"ref_5","first-page":"249","article-title":"Synthesis, characterization and evaluation of anticancer activity of some tetrazole derivatives","volume":"2","author":"Bhaskar","year":"2010","journal-title":"J. Optoelectron. Biomed. Mater."},{"key":"ref_6","first-page":"13","article-title":"Analgesic activity of some 1,2,4-triazole heterocycles clubbed with pyrazole, tetrazole, isoxazole and pyrimidine","volume":"3","author":"Khanage","year":"2013","journal-title":"Adv. Pharm. Bull."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1073","DOI":"10.3389\/fphys.2018.01073","article-title":"The Newly Synthesized Pyrazole Derivative 5-(1-(3 Fluorophenyl)-1H-Pyrazol-4-yl)-2H-Tetrazole Reduces Blood Pressure of Spontaneously Hypertensive Rats via NO-cGMO Pathway","volume":"9","author":"Trindade","year":"2018","journal-title":"Front. Physiol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"775","DOI":"10.1007\/s11224-011-9755-6","article-title":"Computational studies on tetrazole derivatives as potential high energy materials","volume":"22","author":"Ghule","year":"2011","journal-title":"Struct. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"e3733","DOI":"10.1002\/poc.3733","article-title":"Computational design of tetrazolone-based high-energy density energetic materials: Property prediction and decomposition mechanism","volume":"31","author":"Shi","year":"2018","journal-title":"J. Phys. Org. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"10299","DOI":"10.1002\/anie.201502919","article-title":"1, 5-Di (nitramino) Tetrazole: High Sensitivity and Superior Explosive Performance","volume":"54","author":"Fischer","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"188","DOI":"10.1002\/prep.200600026","article-title":"Synthesis and Characterization of 1,4-Dimethyl-5-Aminotetrazolium 5-Nitrotetrazolate","volume":"31","author":"Karaghiosoff","year":"2006","journal-title":"Propellants Explos. Pyrotech. Int. J. Deal. Sci. Technol. Asp. Energ. Mater."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"272","DOI":"10.1039\/c2pp25210d","article-title":"Photochemistry of 1-allyl-4-aryltetrazolones in solution; Structural effects on photoproduct selectivity","volume":"12","author":"Ismael","year":"2013","journal-title":"Photochem. Photobiol. Sci."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"409","DOI":"10.1002\/jhet.5570090240","article-title":"A facile synthesis of 9H-pyrimido [4,5-b] indole via photolysis of 4-azido-5-phenylpyrimidine","volume":"9","author":"Hyatt","year":"1972","journal-title":"J. Heterocycl. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"3757","DOI":"10.3390\/molecules15053757","article-title":"Photochemical transformations of tetrazole derivatives: Applications in organic synthesis","volume":"15","author":"Frija","year":"2010","journal-title":"Molecules"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"317","DOI":"10.1002\/(SICI)1099-0690(199802)1998:2<317::AID-EJOC317>3.0.CO;2-A","article-title":"Photoextrusion of Molecular Nitrogen from Annulated 5-Alkylidene-4, 5-dihydro-1H-tetrazoles: Annulated Iminoaziridines and the First Triplet Diazatrimethylenemethane","volume":"28","author":"Quast","year":"1998","journal-title":"Eur. J. Org. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"526","DOI":"10.1002\/cber.19851180213","article-title":"Photochemische Stickstoff-Eliminierung aus 1, 4-Dihydro-1-phenyl-5H-tetrazol-5-onen und-thionen. Benzimidazolone und Carbodiimide","volume":"118","author":"Quast","year":"1985","journal-title":"Chem. Berichte"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1046","DOI":"10.1039\/b718104c","article-title":"Photochemistry of 5-allyloxy-tetrazoles: Steady-state and laser flash photolysis study","volume":"6","author":"Frija","year":"2008","journal-title":"Org. Biomol. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3583","DOI":"10.1021\/jo060164j","article-title":"Mechanistic investigations into the photochemistry of 4-allyl-tetrazolones in solution: A new approach to the synthesis of 3,4-dihydro-pyrimidinones","volume":"71","author":"Frija","year":"2006","journal-title":"J. Org. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1170","DOI":"10.1039\/b703961a","article-title":"UV-induced photochemistry of matrix-isolated 1-phenyl-4-allyl-tetrazolone","volume":"6","author":"Frija","year":"2007","journal-title":"Photochem. Photobiol. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"259","DOI":"10.1016\/0040-4020(89)80053-5","article-title":"The photochemistry of 1,4-dihtdro-5h-tetrazole derivatives isolated in low-temperature matrices","volume":"45","author":"Dunkin","year":"1989","journal-title":"Tetrahedron"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"3253","DOI":"10.1002\/cber.19811141007","article-title":"Synthese und Photolyse von 1, 4-Dialkyl-1, 4-dihydro-5H-tetrazol-5-onen und-thionen: Neue Wege zu Diaziridinonen und Carbodiimiden1","volume":"114","author":"Quast","year":"1981","journal-title":"Chem. Berichte"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"7967","DOI":"10.1021\/jp0517706","article-title":"Molecular structure, vibrational spectra and photochemistry of 2-methyl-2H-tetrazol-5-amine in solid argon","volume":"109","author":"Reva","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1016\/j.jphotochem.2005.08.021","article-title":"Photochemistry of 1-phenyl-tetrazolone isolated in solid argon","volume":"179","author":"Reva","year":"2006","journal-title":"J. Photochem. Photobiol. A Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"13076","DOI":"10.1021\/jp109215q","article-title":"Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol","volume":"114","author":"Ismael","year":"2010","journal-title":"J. Phys. Chem. A"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"216","DOI":"10.1021\/jo1019859","article-title":"Clean photodecomposition of 1-methyl-4-phenyl-1 H-tetrazole-5 (4 H)-thiones to carbodiimides proceeds via a biradical","volume":"76","author":"Alawode","year":"2011","journal-title":"J. Org. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"6757","DOI":"10.1016\/j.tetlet.2005.07.101","article-title":"Novel efficient synthesis of 3,4-dihydro-6-substituted-3-phenylpyrimidin-2(1H)-ones","volume":"46","author":"Frija","year":"2005","journal-title":"Tetrahedron Lett."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1016\/S0009-2614(99)01149-5","article-title":"Time-dependent density functional theory within the Tamm-Dancoff approximation","volume":"314","author":"Hirata","year":"1999","journal-title":"Chem. Phys. Lett."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other function","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Accounts"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"6158","DOI":"10.1063\/1.478522","article-title":"Toward reliable density functional methods without adjustable parameters: The PBE0 model","volume":"110","author":"Adamo","year":"1999","journal-title":"J. Chem. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1007","DOI":"10.1063\/1.456153","article-title":"Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen","volume":"90","author":"Dunning","year":"1989","journal-title":"J. Chem. Phys."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/0301-0104(81)85090-2","article-title":"Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects","volume":"55","author":"Scrocco","year":"1981","journal-title":"Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1449","DOI":"10.1002\/jcc.20072","article-title":"Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: New energy gradients and molecular surface tessellation","volume":"25","author":"Li","year":"2004","journal-title":"J. Comput. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"154102","DOI":"10.1063\/5.0005188","article-title":"Recent developments in the general atomic and molecular electronic structure system","volume":"152","author":"Barca","year":"2020","journal-title":"J. Chem. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2161","DOI":"10.1021\/cr960149m","article-title":"Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics","volume":"99","author":"Cramer","year":"1999","journal-title":"Chem. Rev."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2019","DOI":"10.1002\/qua.24438","article-title":"TD-DFT benchmarks: A review","volume":"113","author":"Laurent","year":"2013","journal-title":"Int. J. Quantum Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1121","DOI":"10.1021\/acs.jctc.5b00782","article-title":"Evaluation of the Performance of the B3LYP, PBE0, and M06 DFT Functionals, and DBLOC-Corrected Versions, in the Calculation of Redox Potentials and Spin Splittings for Transition Metal Containing Systems","volume":"12","author":"Coskun","year":"2016","journal-title":"J. Chem. Theory Comput."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.cplett.2004.06.011","article-title":"A new hybrid exchange-correlation functional using the Coulomb-attenuating method (CAM-B3LYP)","volume":"393","author":"Yanai","year":"2004","journal-title":"Chem. Phys. Lett."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"10089","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"8425","DOI":"10.1063\/1.1688752","article-title":"A long-range-corrected time-dependent density functional theory","volume":"120","author":"Tawada","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"6615","DOI":"10.1039\/b810189b","article-title":"Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections","volume":"10","author":"Chai","year":"2008","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1456","DOI":"10.1002\/jcc.21759","article-title":"Effect of the damping function in dispersion corrected density functional theory","volume":"32","author":"Grimme","year":"2011","journal-title":"J. Comput. Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"616","DOI":"10.1039\/b300049d","article-title":"Calculation of triplet-triplet energy transfer rates from emission and absorption spectra. The quenching of hemicarcerated triplet biacetyl by aromatic hydrocarbons","volume":"2","author":"Serpa","year":"2003","journal-title":"Photochem. Photobiol. Sci."},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Mckinlay, R.G., Zurek, J.M., and Paterson, M.J. (2010). Vibronic Coupling in Inorganic Systems. Photochemistry, Conical Intersections, and the Jahn-Teller and Pseudo-Jahn-Teller Effects, Academic Press.","DOI":"10.1016\/S0898-8838(10)62009-0"},{"key":"ref_46","doi-asserted-by":"crossref","unstructured":"Rehmat, N., Kurganskii, I.V., Mahmood, Z., Guan, Q.L., Zhao, J., Xing, Y.H., Gurzadyan, G.G., and Fedin, M.V. (2021). Spin\u2013Orbit Charge-Transfer Intersystem Crossing in Anthracene\u2013Perylenebisimide Compact Electron Donor\u2013Acceptor Dyads and Triads and Photochemical Dianion Formation. Chem. Eur. J.","DOI":"10.1002\/chem.202005285"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"104513","DOI":"10.1063\/1.1867373","article-title":"Electronic excitation energies of molecules in solution: State specific and linear response methods for nonequilibrium continuum solvation models","volume":"122","author":"Cammi","year":"2005","journal-title":"J. Chem. Phys."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1021\/ct700187z","article-title":"TD-DFT performance for the visible absorption spectra of organic dyes: Conventional versus long-range hybrids","volume":"4","author":"Jacquemin","year":"2008","journal-title":"J. Chem. Theory Comput."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"4157","DOI":"10.1021\/jp501974p","article-title":"How method-dependent are calculated differences between vertical, adiabatic, and 0-0 excitation energies?","volume":"118","author":"Fang","year":"2014","journal-title":"J. Phys. Chem. A"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"360","DOI":"10.3390\/i3040360","article-title":"Can Unrestricted Density-Functional Theory Describe Open Shell Singlet Biradicals?","volume":"3","author":"Kraka","year":"2002","journal-title":"Int. J. Mol. Sci."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"11302","DOI":"10.1021\/jp072027b","article-title":"Ab initio molecular dynamics of excited-state intramolecular proton transfer using multireference perturbation theory","volume":"111","author":"Coe","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2228","DOI":"10.1002\/jcc.26384","article-title":"Ab-initio molecular dynamics and hybrid explicit-implicit solvation model for aqueous and nonaqueous solvents: GFP chromophore in water and methanol solution as case study","volume":"41","author":"Raucci","year":"2020","journal-title":"J. Comput. Chem."}],"container-title":["Applied Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2076-3417\/11\/9\/4045\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T05:55:08Z","timestamp":1760162108000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2076-3417\/11\/9\/4045"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,4,29]]},"references-count":52,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2021,5]]}},"alternative-id":["app11094045"],"URL":"https:\/\/doi.org\/10.3390\/app11094045","relation":{},"ISSN":["2076-3417"],"issn-type":[{"value":"2076-3417","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,4,29]]}}}