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Article: Ultrafast Adiabatic Photodehydration of 2-Hydroxymethylphenol and the Formation of Quinone Methide

TitleUltrafast Adiabatic Photodehydration of 2-Hydroxymethylphenol and the Formation of Quinone Methide
Authors
Keywordscryochemistry
density functional calculations
photochemistry
quinone methides
transient spectroscopy
Issue Date2018
PublisherWiley - VCH Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2018, v. 24 n. 37, p. 9426-9435 How to Cite?
AbstractThe photochemical reactivity of 2-hydroxymethylphenol (1) was investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. In addition, theoretical studies were performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway to obtain a better understanding of the reaction mechanism. The main finding of this work is that photodehydration of 1 takes place in an ultrafast adiabatic photochemical reaction without any clear intermediate, delivering quinone methide (QM) in the excited state. Upon photoexcitation to a higher vibrational level of the singlet excited state, 1 undergoes vibrational relaxation leading to two photochemical pathways, one by which synchronous elimination of H2O gives QM 2 in its S1 state and the other by which homolytic cleavage of the phenolic O−H bond produces a phenoxyl radical (S0). Both are ultrafast processes that occur within a picosecond. The excited state of QM 2 (S1) probably deactivates to S0 through a conical intersection to give QM 2 (S0), which subsequently delivers benzoxete 4. Elucidation of the reaction mechanisms for the photodehydration of phenols by which QMs are formed is important to tune the reactivity of QMs with DNA and proteins for the potential application of QMs in medicine as therapeutic agents. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Persistent Identifierhttp://hdl.handle.net/10722/279291
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorŠkalamera, D-
dc.contributor.authorAntol, I-
dc.contributor.authorMlinarić-Majerski, K-
dc.contributor.authorVančik, H-
dc.contributor.authorPhillips, DL-
dc.contributor.authorMa, J-
dc.contributor.authorBasarić, N-
dc.date.accessioned2019-10-25T02:13:13Z-
dc.date.available2019-10-25T02:13:13Z-
dc.date.issued2018-
dc.identifier.citationChemistry - A European Journal, 2018, v. 24 n. 37, p. 9426-9435-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/279291-
dc.description.abstractThe photochemical reactivity of 2-hydroxymethylphenol (1) was investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. In addition, theoretical studies were performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway to obtain a better understanding of the reaction mechanism. The main finding of this work is that photodehydration of 1 takes place in an ultrafast adiabatic photochemical reaction without any clear intermediate, delivering quinone methide (QM) in the excited state. Upon photoexcitation to a higher vibrational level of the singlet excited state, 1 undergoes vibrational relaxation leading to two photochemical pathways, one by which synchronous elimination of H2O gives QM 2 in its S1 state and the other by which homolytic cleavage of the phenolic O−H bond produces a phenoxyl radical (S0). Both are ultrafast processes that occur within a picosecond. The excited state of QM 2 (S1) probably deactivates to S0 through a conical intersection to give QM 2 (S0), which subsequently delivers benzoxete 4. Elucidation of the reaction mechanisms for the photodehydration of phenols by which QMs are formed is important to tune the reactivity of QMs with DNA and proteins for the potential application of QMs in medicine as therapeutic agents. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim-
dc.languageeng-
dc.publisherWiley - VCH Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry-
dc.relation.ispartofChemistry - A European Journal-
dc.rightsThis is the peer reviewed version of the following article: [FULL CITE], which has been published in final form at [Link to final article using the DOI]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.-
dc.subjectcryochemistry-
dc.subjectdensity functional calculations-
dc.subjectphotochemistry-
dc.subjectquinone methides-
dc.subjecttransient spectroscopy-
dc.titleUltrafast Adiabatic Photodehydration of 2-Hydroxymethylphenol and the Formation of Quinone Methide-
dc.typeArticle-
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.authorityPhillips, DL=rp00770-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.201801543-
dc.identifier.pmid29677402-
dc.identifier.scopuseid_2-s2.0-85049354950-
dc.identifier.hkuros308134-
dc.identifier.volume24-
dc.identifier.issue37-
dc.identifier.spage9426-
dc.identifier.epage9435-
dc.identifier.isiWOS:000436934300033-
dc.publisher.placeGermany-
dc.identifier.issnl0947-6539-

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