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Article: Reaction mechanisms and structural characterization of the reactive intermediates observed after the photolysis of 3-(hydroxymethyl)benzophenone in acetonitrile, 2-propanol, and neutral and acidic aqueous solutions

TitleReaction mechanisms and structural characterization of the reactive intermediates observed after the photolysis of 3-(hydroxymethyl)benzophenone in acetonitrile, 2-propanol, and neutral and acidic aqueous solutions
Authors
KeywordsAqueous solutions
Density functional theory
Triplet state
Photoinduced reaction
Raman spectrometry
Issue Date2011
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2011, v. 76 n. 10, p. 3710-3719 How to Cite?
AbstractNanosecond time-resolved resonance Raman (ns-TR3) spectroscopy was employed to investigate the photoinduced reactions of 3-(hydroxymethyl) benzophenone (1) in acetonitrile, 2-propanol, and neutral and acidic aqueous solutions. Density functional theory calculations were utilized to help the interpretation of the experimental spectra. In acetonitrile, the neutral triplet state 1 [denoted here as (m-BPOH)3] was observed on the nanosecond to microsecond time scale. In 2-propanol this triplet state appeared to abstract a hydrogen atom from the solvent molecules to produce the aryphenyl ketyl radical of 1 (denoted here as ArPK of 1), and then this species underwent a cross-coupling reaction with the dimethylketyl radical (also formed from the hydrogen abstraction reaction) to form a long-lived light absorbing transient species that was tentatively identified to be mainly 2-(4-(hydroxy(3- (hydroxymethyl)phenyl)methylene)cyclohexa-2,5-dienyl)propan-2-ol. In 1:1 H 2O:CH3CN aqueous solution at neutral pH, (m-BPOH) 3 reacted with water to produce the ArPK of 1 and then underwent further reaction to produce a long-lived light absorbing transient species. Three photochemical reactions appeared to take place after 266 nm photolysis of 1 in acidic aqueous solutions, a photoreduction reaction, an overall photohydration reaction, and a novel photoredox reaction. TR3 experiments in 1:1 H2O:CH3CN aqueous solution at pH 2 detected a new triplet biradical species, which is associated with an unusual photoredox reaction. This reaction is observed to be the predominant reaction at pH 2 and seems to face competition from the overall photohydration reaction at pH 0. © 2011 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/138985
ISSN
2014 Impact Factor: 4.721
2014 SCImago Journal Rankings: 1.777
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council of Hong KongHKU 7035/08P
Croucher Foundation
University of Hong Kong
University Grants Committee Areas of Excellence SchemeAoE/P-03/08
Special Equipment Grant (SEG)HKU/07
Funding Information:

The research was supported by grants from the Research Grants Council of Hong Kong (HKU 7035/08P) to D.L.P. D.L. P. thanks the Croucher Foundation for the Award of a Senior Research Fellowship and the University of Hong Kong for the Outstanding Researcher Award. Support from the University Grants Committee Areas of Excellence Scheme (AoE/P-03/08) and the Special Equipment Grant (SEG HKU/07) is also gratefully acknowledged.

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DC FieldValueLanguage
dc.contributor.authorMa, Jen_HK
dc.contributor.authorLi, MDen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorWan, Pen_HK
dc.date.accessioned2011-09-23T05:43:39Z-
dc.date.available2011-09-23T05:43:39Z-
dc.date.issued2011en_HK
dc.identifier.citationJournal Of Organic Chemistry, 2011, v. 76 n. 10, p. 3710-3719en_HK
dc.identifier.issn0022-3263en_HK
dc.identifier.urihttp://hdl.handle.net/10722/138985-
dc.description.abstractNanosecond time-resolved resonance Raman (ns-TR3) spectroscopy was employed to investigate the photoinduced reactions of 3-(hydroxymethyl) benzophenone (1) in acetonitrile, 2-propanol, and neutral and acidic aqueous solutions. Density functional theory calculations were utilized to help the interpretation of the experimental spectra. In acetonitrile, the neutral triplet state 1 [denoted here as (m-BPOH)3] was observed on the nanosecond to microsecond time scale. In 2-propanol this triplet state appeared to abstract a hydrogen atom from the solvent molecules to produce the aryphenyl ketyl radical of 1 (denoted here as ArPK of 1), and then this species underwent a cross-coupling reaction with the dimethylketyl radical (also formed from the hydrogen abstraction reaction) to form a long-lived light absorbing transient species that was tentatively identified to be mainly 2-(4-(hydroxy(3- (hydroxymethyl)phenyl)methylene)cyclohexa-2,5-dienyl)propan-2-ol. In 1:1 H 2O:CH3CN aqueous solution at neutral pH, (m-BPOH) 3 reacted with water to produce the ArPK of 1 and then underwent further reaction to produce a long-lived light absorbing transient species. Three photochemical reactions appeared to take place after 266 nm photolysis of 1 in acidic aqueous solutions, a photoreduction reaction, an overall photohydration reaction, and a novel photoredox reaction. TR3 experiments in 1:1 H2O:CH3CN aqueous solution at pH 2 detected a new triplet biradical species, which is associated with an unusual photoredox reaction. This reaction is observed to be the predominant reaction at pH 2 and seems to face competition from the overall photohydration reaction at pH 0. © 2011 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jocen_HK
dc.relation.ispartofJournal of Organic Chemistryen_HK
dc.subjectAqueous solutions-
dc.subjectDensity functional theory-
dc.subjectTriplet state-
dc.subjectPhotoinduced reaction-
dc.subjectRaman spectrometry-
dc.titleReaction mechanisms and structural characterization of the reactive intermediates observed after the photolysis of 3-(hydroxymethyl)benzophenone in acetonitrile, 2-propanol, and neutral and acidic aqueous solutionsen_HK
dc.typeArticleen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jo1024249en_HK
dc.identifier.pmid21466158-
dc.identifier.scopuseid_2-s2.0-79956135687en_HK
dc.identifier.hkuros194539en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-79956135687&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume76en_HK
dc.identifier.issue10en_HK
dc.identifier.spage3710en_HK
dc.identifier.epage3719en_HK
dc.identifier.isiWOS:000290465700011-
dc.publisher.placeUnited Statesen_HK
dc.relation.projectInstitute of Molecular Functional Materials-
dc.identifier.scopusauthoridMa, J=39161647600en_HK
dc.identifier.scopusauthoridLi, MD=35173063700en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridWan, P=7103181978en_HK

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