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Article: Time-resolved resonance Raman and density functional theory study of the deprotonation reaction of the triplet state of para-hydroxybenzophenone in mixed acetonitrile/water solutions

TitleTime-resolved resonance Raman and density functional theory study of the deprotonation reaction of the triplet state of para-hydroxybenzophenone in mixed acetonitrile/water solutions
Authors
KeywordsAnion
Density functional theory (DFT)
Para-hydroxybenzophenone (p-HBP)
Resonance Raman spectroscopy
Time-resolved
Triplet state
Issue Date2008
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, 2008, v. 39 n. 11, p. 1518-1525 How to Cite?
AbstractNanosecond time-resolved resonance Raman (ns-TR 3) spectroscopy was employed to investigate the triplet state of para-hydroxybenzophenone (p-hBP) in pure acetonitrile (MeCN) and its subsequent deprotonation reaction in a H 2O/MeCN mixed solution. The TR 3 results reveal that the deprotonation reaction occurred with the p-hBP triplet state as the precursor species after 266 nm photolysis of p-hBP in aH 2O/MeCN mixed solution. The ground-state p-hBP anion species was observed to form about 20 ns after excitation in a 5% H 2O/95% MeCN mixed solvent. Density functional theory (DFT) calculations were done to help obtain information about the structures and vibrational modes of the triplet p-hBP and p-hBP anion species. A reaction scheme is proposed for the photoreaction pathways of p-hBP in pure MeCN and H 2O/MeCN mixed solvents. Comparison of the results here for p-hBP to the related para-hydroxyacetophenone (HA) system indicates that substitution of the methyl group in HA with a phenyl group to form p-hBP significantly alters the chemical reactivity of the triplet state so that both deprotonation and intersystem crossing (ISC) for the triplet state occur much faster in p-hBP than in HA. Copyright © 2008 John Wiley & Sons, Ltd.
Persistent Identifierhttp://hdl.handle.net/10722/58387
ISSN
2015 Impact Factor: 2.395
2015 SCImago Journal Rankings: 1.075
ISI Accession Number ID
Funding AgencyGrant Number
HKU
Research Grants Council of Hong KongPolyU 7029/06P
PolyU 7029/07P
HKU/7040/06P
Croucher Foundation
Funding Information:

This research has been supported by funding from HKU [Seed Funding Program for Basic Research 2007-2008 to WMK and an Outstanding Researcher Award (2006) to DLP] and from the Research Grants Council of Hong Kong (PolyU 7029/06P and PolyU 7029/07P to WMK and HKU/7040/06P to DLP). WMK thanks HKU for the award of an RAP and DLP thanks the Croucher Foundation for a Croucher Foundation Senior Research Fellowship (2006-2007).

References

 

DC FieldValueLanguage
dc.contributor.authorDu, Yen_HK
dc.contributor.authorXue, Jen_HK
dc.contributor.authorMa, Cen_HK
dc.contributor.authorKwok, WMen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-05-31T03:29:24Z-
dc.date.available2010-05-31T03:29:24Z-
dc.date.issued2008en_HK
dc.identifier.citationJournal Of Raman Spectroscopy, 2008, v. 39 n. 11, p. 1518-1525en_HK
dc.identifier.issn0377-0486en_HK
dc.identifier.urihttp://hdl.handle.net/10722/58387-
dc.description.abstractNanosecond time-resolved resonance Raman (ns-TR 3) spectroscopy was employed to investigate the triplet state of para-hydroxybenzophenone (p-hBP) in pure acetonitrile (MeCN) and its subsequent deprotonation reaction in a H 2O/MeCN mixed solution. The TR 3 results reveal that the deprotonation reaction occurred with the p-hBP triplet state as the precursor species after 266 nm photolysis of p-hBP in aH 2O/MeCN mixed solution. The ground-state p-hBP anion species was observed to form about 20 ns after excitation in a 5% H 2O/95% MeCN mixed solvent. Density functional theory (DFT) calculations were done to help obtain information about the structures and vibrational modes of the triplet p-hBP and p-hBP anion species. A reaction scheme is proposed for the photoreaction pathways of p-hBP in pure MeCN and H 2O/MeCN mixed solvents. Comparison of the results here for p-hBP to the related para-hydroxyacetophenone (HA) system indicates that substitution of the methyl group in HA with a phenyl group to form p-hBP significantly alters the chemical reactivity of the triplet state so that both deprotonation and intersystem crossing (ISC) for the triplet state occur much faster in p-hBP than in HA. Copyright © 2008 John Wiley & Sons, Ltd.en_HK
dc.languageengen_HK
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.rightsJournal of Raman Spectroscopy . Copyright © John Wiley & Sons Ltd.en_HK
dc.subjectAnionen_HK
dc.subjectDensity functional theory (DFT)en_HK
dc.subjectPara-hydroxybenzophenone (p-HBP)en_HK
dc.subjectResonance Raman spectroscopyen_HK
dc.subjectTime-resolveden_HK
dc.subjectTriplet stateen_HK
dc.titleTime-resolved resonance Raman and density functional theory study of the deprotonation reaction of the triplet state of para-hydroxybenzophenone in mixed acetonitrile/water solutionsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0377-0486&volume=39&spage=1518&epage=1525&date=2008&atitle=Time-resolved+Resonance+Raman+and+Density+Functional+Theory+Study+of+the+Deprotonation+Reaction+of+the+Triplet+State+of+Para-hydroxybenzophenone+in+Mixed+Acetonitrile+/+Water+Solutionsen_HK
dc.identifier.emailMa, C:macs@hkucc.hku.hken_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityMa, C=rp00758en_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/jrs.1997en_HK
dc.identifier.scopuseid_2-s2.0-55449127953en_HK
dc.identifier.hkuros157125en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-55449127953&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume39en_HK
dc.identifier.issue11en_HK
dc.identifier.spage1518en_HK
dc.identifier.epage1525en_HK
dc.identifier.isiWOS:000261206200005-
dc.publisher.placeUnited Kingdomen_HK
dc.identifier.scopusauthoridDu, Y=35310175500en_HK
dc.identifier.scopusauthoridXue, J=23007272500en_HK
dc.identifier.scopusauthoridMa, C=7402924979en_HK
dc.identifier.scopusauthoridKwok, WM=7103129332en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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