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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

TitleInfluence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: A time-resolved resonance Raman and density functional theory study
Authors
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
Citation
Journal Of Raman Spectroscopy, 2012, v. 43 n. 6, p. 774-780 How to Cite?
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.
Persistent Identifierhttp://hdl.handle.net/10722/159298
ISSN
2015 Impact Factor: 2.395
2015 SCImago Journal Rankings: 1.075
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLi, Wen_HK
dc.contributor.authorXue, Jen_HK
dc.contributor.authorCheng, SCen_HK
dc.contributor.authorDu, Yen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2012-08-16T05:48:29Z-
dc.date.available2012-08-16T05:48:29Z-
dc.date.issued2012en_HK
dc.identifier.citationJournal Of Raman Spectroscopy, 2012, v. 43 n. 6, p. 774-780en_HK
dc.identifier.issn0377-0486en_HK
dc.identifier.urihttp://hdl.handle.net/10722/159298-
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.en_HK
dc.languageengen_US
dc.publisherJohn Wiley & Sons Ltd. The Journal's web site is located at http://www3.interscience.wiley.com/cgi-bin/jhome/3420en_HK
dc.relation.ispartofJournal of Raman Spectroscopyen_HK
dc.subjectchloro-substituted benzophenoneen_HK
dc.subjecthydrogen abstractionen_HK
dc.subjectketyl radicalen_HK
dc.subjecttime-resolved resonance Raman spectroscopyen_HK
dc.subjecttriplet stateen_HK
dc.titleInfluence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: A time-resolved resonance Raman and density functional theory studyen_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.doi10.1002/jrs.3078en_HK
dc.identifier.scopuseid_2-s2.0-84862566538en_HK
dc.identifier.hkuros203414en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-84862566538&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume43en_HK
dc.identifier.issue6en_HK
dc.identifier.spage774en_HK
dc.identifier.epage780en_HK
dc.identifier.isiWOS:000305391800016-
dc.publisher.placeUnited Kingdomen_HK
dc.identifier.scopusauthoridLi, W=53877655000en_HK
dc.identifier.scopusauthoridXue, J=23007272500en_HK
dc.identifier.scopusauthoridCheng, SC=53877096300en_HK
dc.identifier.scopusauthoridDu, Y=35310175500en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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