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Article: Femtosecond transient absorption and nanosecond time-resolved resonance raman study of the solvent-dependent photo-deprotection reaction of benzoin diethyl phosphate

TitleFemtosecond transient absorption and nanosecond time-resolved resonance raman study of the solvent-dependent photo-deprotection reaction of benzoin diethyl phosphate
Authors
KeywordsRaman spectroscopy
Solvent effects
Time-resolved spectroscopy
Transient absorption
Issue Date2007
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2007, v. 13 n. 8, p. 2290-2305 How to Cite?
AbstractA combined femtosecond transient absorption (fs-TA) and nanosecond time-resolved resonance Raman (ns-TR 3) study was performed to directly detect the dynamics and elucidate the mechanism of the excited state deactivation and solvent-dependent photo-deprotection pathways for benzoin diethyl phosphate (BDP) in neat acetonitrile (MeCN) and 75% H 2O/25% MeCN. Comparison of the TA spectral evolution observed in the two solvents provides explicit evidence that the photophysical deactivation of the BDP singlet excited state has little solvent dependence. The TA spectra also indicate the related internal conversion (IC) and intersystem crossing (ISC) processes occur rapidly on hundreds of femtoseconds and ∼2-3 ps time scales, respectively. From this and in conjunction with a photochemistry study and ground state resonance Raman (RR) measurements, the TA results reveal that the phenacyl localized BDP triplet state (that is mainly nπ* nature) is the common and immediate precursor to the photo-deprotection reaction in both solvents. However, the triplet deprotection follows different pathways in neat MeCN versus the largely water containing solvent. The deprotection reaction in MeCN was determined to occur with a ∼1 ns time constant and the reaction was found to be an unimolecular process leading to elimination of the diethyl phosphoric acid apparently concurrent with cyclization to yield the benzofuran product. In the water mixed solvent, the triplet reaction was observed to proceed with a ∼15 ns time constant and the reaction leads to not only the deprotection-cyclization but also a heterolytic dissociation to release the diethyl phosphate anion through a branching and competing mechanism. The ns-TR 3 spectra combined with relevant DFT calculations have been used to characterize the dynamics, structure and vibrational frequencies to help identify the important intermediates as well as to explore the reaction pathway leading to formation of the solvolysis product in the largely water solvent. A consecutive mechanism has been revealed for the heterolysis-solvolysis reaction in the water mixed solvent. The present work provides direct and irrevocable evidence for the dynamics and mechanistic description of the overall photophysics and deprotection related photochemistry for BDP. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/70269
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorMa, Cen_HK
dc.contributor.authorDu, Yen_HK
dc.contributor.authorKwok, WMen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:21:18Z-
dc.date.available2010-09-06T06:21:18Z-
dc.date.issued2007en_HK
dc.identifier.citationChemistry - A European Journal, 2007, v. 13 n. 8, p. 2290-2305en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70269-
dc.description.abstractA combined femtosecond transient absorption (fs-TA) and nanosecond time-resolved resonance Raman (ns-TR 3) study was performed to directly detect the dynamics and elucidate the mechanism of the excited state deactivation and solvent-dependent photo-deprotection pathways for benzoin diethyl phosphate (BDP) in neat acetonitrile (MeCN) and 75% H 2O/25% MeCN. Comparison of the TA spectral evolution observed in the two solvents provides explicit evidence that the photophysical deactivation of the BDP singlet excited state has little solvent dependence. The TA spectra also indicate the related internal conversion (IC) and intersystem crossing (ISC) processes occur rapidly on hundreds of femtoseconds and ∼2-3 ps time scales, respectively. From this and in conjunction with a photochemistry study and ground state resonance Raman (RR) measurements, the TA results reveal that the phenacyl localized BDP triplet state (that is mainly nπ* nature) is the common and immediate precursor to the photo-deprotection reaction in both solvents. However, the triplet deprotection follows different pathways in neat MeCN versus the largely water containing solvent. The deprotection reaction in MeCN was determined to occur with a ∼1 ns time constant and the reaction was found to be an unimolecular process leading to elimination of the diethyl phosphoric acid apparently concurrent with cyclization to yield the benzofuran product. In the water mixed solvent, the triplet reaction was observed to proceed with a ∼15 ns time constant and the reaction leads to not only the deprotection-cyclization but also a heterolytic dissociation to release the diethyl phosphate anion through a branching and competing mechanism. The ns-TR 3 spectra combined with relevant DFT calculations have been used to characterize the dynamics, structure and vibrational frequencies to help identify the important intermediates as well as to explore the reaction pathway leading to formation of the solvolysis product in the largely water solvent. A consecutive mechanism has been revealed for the heterolysis-solvolysis reaction in the water mixed solvent. The present work provides direct and irrevocable evidence for the dynamics and mechanistic description of the overall photophysics and deprotection related photochemistry for BDP. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectRaman spectroscopyen_HK
dc.subjectSolvent effectsen_HK
dc.subjectTime-resolved spectroscopyen_HK
dc.subjectTransient absorptionen_HK
dc.titleFemtosecond transient absorption and nanosecond time-resolved resonance raman study of the solvent-dependent photo-deprotection reaction of benzoin diethyl phosphateen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=13&issue=8&spage=2290&epage=2305&date=2007&atitle=Femtosecond+transient+absorption+and+nanosecond+time-resolved+resonance+Raman+study+of+the+solvent-dependent+photo-deprotection+reaction+of+benzoin+diethyl+phosphateen_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/chem.200600893en_HK
dc.identifier.pmid17154320-
dc.identifier.scopuseid_2-s2.0-34250659166en_HK
dc.identifier.hkuros133777en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-34250659166&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume13en_HK
dc.identifier.issue8en_HK
dc.identifier.spage2290en_HK
dc.identifier.epage2305en_HK
dc.identifier.isiWOS:000244805500015-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridMa, C=7402924979en_HK
dc.identifier.scopusauthoridDu, Y=35310175500en_HK
dc.identifier.scopusauthoridKwok, WM=7103129332en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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