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Article: Influence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: A time-resolved resonance Raman and density functional theory study
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TitleInfluence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: A time-resolved resonance Raman and density functional theory study
 
AuthorsLi, W1
Xue, J1
Cheng, SC1
Du, Y2
Phillips, DL1
 
Keywordschloro-substituted benzophenone
hydrogen abstraction
ketyl radical
time-resolved resonance Raman spectroscopy
triplet state
 
Issue Date2012
 
PublisherJohn Wiley & Sons Ltd. The Journal's web site is located at http://www3.interscience.wiley.com/cgi-bin/jhome/3420
 
CitationJournal Of Raman Spectroscopy, 2012, v. 43 n. 6, p. 774-780 [How to Cite?]
DOI: http://dx.doi.org/10.1002/jrs.3078
 
AbstractA nanosecond time-resolved resonance Raman (ns-TR 3) spectroscopic investigation of the photoreduction reactions and ability of several chloro-substituted benzophenone (Cl-BP) triplets is described. The TR 3 results show that the 3-chlorobenzophenone (3-Cl-BP), 4-chlorobenzophenone (4-Cl-BP) and 4,4'-dichlorobenzophenone (4,4'-dichloro-BP) triplets exhibit similar hydrogen abstraction ability with the parent BP triplet. In 2-propanol, the 3-Cl-, 4-Cl- and 4,4'-dichloro-diphenylketyl (DPK) radicals were observed and they appear to react with dimethylketyl radicals at the para-position to form a light absorption transient species. These transient species were characterized with TR 3 spectra, and identified with the help of results from density functional theory calculations. In an acetontitrile/water (MeCN:H 2O) 1:1 mixed solvent, these DPK radicals were also observed but with slower formation rates. However, the 2-Cl-DPK radical was observed to form with a lower yield and a significantly slower formation rate than the other chloro-substituted benzophenones examined here in 2-propanol under the same experimental conditions. These results reveal that the 2-chloro substituent reduces the hydrogen abstraction ability of the substituted BP triplet, which was not as expected based on the assumption that the electron-withdrawing group could increase its photoreduction ability. This unusual ortho effect of the chlorine substitution is briefly discussed. Copyright © 2011 John Wiley & Sons, Ltd.
 
ISSN0377-0486
2013 Impact Factor: 2.519
 
DOIhttp://dx.doi.org/10.1002/jrs.3078
 
ReferencesReferences in Scopus
 
DC FieldValue
dc.contributor.authorLi, W
 
dc.contributor.authorXue, J
 
dc.contributor.authorCheng, SC
 
dc.contributor.authorDu, Y
 
dc.contributor.authorPhillips, DL
 
dc.date.accessioned2012-08-16T05:48:29Z
 
dc.date.available2012-08-16T05:48:29Z
 
dc.date.issued2012
 
dc.description.abstractA nanosecond time-resolved resonance Raman (ns-TR 3) spectroscopic investigation of the photoreduction reactions and ability of several chloro-substituted benzophenone (Cl-BP) triplets is described. The TR 3 results show that the 3-chlorobenzophenone (3-Cl-BP), 4-chlorobenzophenone (4-Cl-BP) and 4,4'-dichlorobenzophenone (4,4'-dichloro-BP) triplets exhibit similar hydrogen abstraction ability with the parent BP triplet. In 2-propanol, the 3-Cl-, 4-Cl- and 4,4'-dichloro-diphenylketyl (DPK) radicals were observed and they appear to react with dimethylketyl radicals at the para-position to form a light absorption transient species. These transient species were characterized with TR 3 spectra, and identified with the help of results from density functional theory calculations. In an acetontitrile/water (MeCN:H 2O) 1:1 mixed solvent, these DPK radicals were also observed but with slower formation rates. However, the 2-Cl-DPK radical was observed to form with a lower yield and a significantly slower formation rate than the other chloro-substituted benzophenones examined here in 2-propanol under the same experimental conditions. These results reveal that the 2-chloro substituent reduces the hydrogen abstraction ability of the substituted BP triplet, which was not as expected based on the assumption that the electron-withdrawing group could increase its photoreduction ability. This unusual ortho effect of the chlorine substitution is briefly discussed. Copyright © 2011 John Wiley & Sons, Ltd.
 
dc.description.natureLink_to_subscribed_fulltext
 
dc.identifier.citationJournal Of Raman Spectroscopy, 2012, v. 43 n. 6, p. 774-780 [How to Cite?]
DOI: http://dx.doi.org/10.1002/jrs.3078
 
dc.identifier.doihttp://dx.doi.org/10.1002/jrs.3078
 
dc.identifier.epage780
 
dc.identifier.hkuros203414
 
dc.identifier.issn0377-0486
2013 Impact Factor: 2.519
 
dc.identifier.issue6
 
dc.identifier.scopuseid_2-s2.0-84862566538
 
dc.identifier.spage774
 
dc.identifier.urihttp://hdl.handle.net/10722/159298
 
dc.identifier.volume43
 
dc.languageeng
 
dc.publisherJohn Wiley & Sons Ltd. The Journal's web site is located at http://www3.interscience.wiley.com/cgi-bin/jhome/3420
 
dc.publisher.placeUnited Kingdom
 
dc.relation.ispartofJournal of Raman Spectroscopy
 
dc.relation.referencesReferences in Scopus
 
dc.subjectchloro-substituted benzophenone
 
dc.subjecthydrogen abstraction
 
dc.subjectketyl radical
 
dc.subjecttime-resolved resonance Raman spectroscopy
 
dc.subjecttriplet state
 
dc.titleInfluence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: A time-resolved resonance Raman and density functional theory study
 
dc.typeArticle
 
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<contributor.author>Du, Y</contributor.author>
<contributor.author>Phillips, DL</contributor.author>
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<description.abstract>A nanosecond time-resolved resonance Raman (ns-TR 3) spectroscopic investigation of the photoreduction reactions and ability of several chloro-substituted benzophenone (Cl-BP) triplets is described. The TR 3 results show that the 3-chlorobenzophenone (3-Cl-BP), 4-chlorobenzophenone (4-Cl-BP) and 4,4&apos;-dichlorobenzophenone (4,4&apos;-dichloro-BP) triplets exhibit similar hydrogen abstraction ability with the parent BP triplet. In 2-propanol, the 3-Cl-, 4-Cl- and 4,4&apos;-dichloro-diphenylketyl (DPK) radicals were observed and they appear to react with dimethylketyl radicals at the para-position to form a light absorption transient species. These transient species were characterized with TR 3 spectra, and identified with the help of results from density functional theory calculations. In an acetontitrile/water (MeCN:H 2O) 1:1 mixed solvent, these DPK radicals were also observed but with slower formation rates. However, the 2-Cl-DPK radical was observed to form with a lower yield and a significantly slower formation rate than the other chloro-substituted benzophenones examined here in 2-propanol under the same experimental conditions. These results reveal that the 2-chloro substituent reduces the hydrogen abstraction ability of the substituted BP triplet, which was not as expected based on the assumption that the electron-withdrawing group could increase its photoreduction ability. This unusual ortho effect of the chlorine substitution is briefly discussed. Copyright &#169; 2011 John Wiley &amp; Sons, Ltd.</description.abstract>
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Author Affiliations
  1. The University of Hong Kong
  2. China Jiliang University