File Download
 
Links for fulltext
(May Require Subscription)
 
Supplementary

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
  • Basic View
  • Metadata View
  • XML View
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
 
AuthorsMa, J1
Li, MD1
Phillips, DL1
Wan, P2
 
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
 
CitationJournal Of Organic Chemistry, 2011, v. 76 n. 10, p. 3710-3719 [How to Cite?]
DOI: http://dx.doi.org/10.1021/jo1024249
 
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.
 
ISSN0022-3263
2013 Impact Factor: 4.638
 
DOIhttp://dx.doi.org/10.1021/jo1024249
 
ISI Accession Number IDWOS:000290465700011
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.

 
ReferencesReferences in Scopus
 
GrantsInstitute of Molecular Functional Materials
 
DC FieldValue
dc.contributor.authorMa, J
 
dc.contributor.authorLi, MD
 
dc.contributor.authorPhillips, DL
 
dc.contributor.authorWan, P
 
dc.date.accessioned2011-09-23T05:43:39Z
 
dc.date.available2011-09-23T05:43:39Z
 
dc.date.issued2011
 
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.
 
dc.description.naturelink_to_subscribed_fulltext
 
dc.identifier.citationJournal Of Organic Chemistry, 2011, v. 76 n. 10, p. 3710-3719 [How to Cite?]
DOI: http://dx.doi.org/10.1021/jo1024249
 
dc.identifier.doihttp://dx.doi.org/10.1021/jo1024249
 
dc.identifier.epage3719
 
dc.identifier.hkuros194539
 
dc.identifier.isiWOS:000290465700011
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.

 
dc.identifier.issn0022-3263
2013 Impact Factor: 4.638
 
dc.identifier.issue10
 
dc.identifier.pmid21466158
 
dc.identifier.scopuseid_2-s2.0-79956135687
 
dc.identifier.spage3710
 
dc.identifier.urihttp://hdl.handle.net/10722/138985
 
dc.identifier.volume76
 
dc.languageeng
 
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
 
dc.publisher.placeUnited States
 
dc.relation.ispartofJournal of Organic Chemistry
 
dc.relation.projectInstitute of Molecular Functional Materials
 
dc.relation.referencesReferences in Scopus
 
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 solutions
 
dc.typeArticle
 
<?xml encoding="utf-8" version="1.0"?>
<item><contributor.author>Ma, J</contributor.author>
<contributor.author>Li, MD</contributor.author>
<contributor.author>Phillips, DL</contributor.author>
<contributor.author>Wan, P</contributor.author>
<date.accessioned>2011-09-23T05:43:39Z</date.accessioned>
<date.available>2011-09-23T05:43:39Z</date.available>
<date.issued>2011</date.issued>
<identifier.citation>Journal Of Organic Chemistry, 2011, v. 76 n. 10, p. 3710-3719</identifier.citation>
<identifier.issn>0022-3263</identifier.issn>
<identifier.uri>http://hdl.handle.net/10722/138985</identifier.uri>
<description.abstract>Nanosecond 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. &#169; 2011 American Chemical Society.</description.abstract>
<language>eng</language>
<publisher>American Chemical Society. The Journal&apos;s web site is located at http://pubs.acs.org/joc</publisher>
<relation.ispartof>Journal of Organic Chemistry</relation.ispartof>
<subject>Aqueous solutions</subject>
<subject>Density functional theory</subject>
<subject>Triplet state</subject>
<subject>Photoinduced reaction</subject>
<subject>Raman spectrometry</subject>
<title>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</title>
<type>Article</type>
<description.nature>link_to_subscribed_fulltext</description.nature>
<identifier.doi>10.1021/jo1024249</identifier.doi>
<identifier.pmid>21466158</identifier.pmid>
<identifier.scopus>eid_2-s2.0-79956135687</identifier.scopus>
<identifier.hkuros>194539</identifier.hkuros>
<relation.references>http://www.scopus.com/mlt/select.url?eid=2-s2.0-79956135687&amp;selection=ref&amp;src=s&amp;origin=recordpage</relation.references>
<identifier.volume>76</identifier.volume>
<identifier.issue>10</identifier.issue>
<identifier.spage>3710</identifier.spage>
<identifier.epage>3719</identifier.epage>
<identifier.isi>WOS:000290465700011</identifier.isi>
<publisher.place>United States</publisher.place>
<relation.project>Institute of Molecular Functional Materials</relation.project>
</item>
Author Affiliations
  1. The University of Hong Kong
  2. University of Victoria