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- PMID: 20684501
- WOS: WOS:000281180100006
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Article: Photophysics and photodeprotection reactions of p-methoxyphenacyl phototriggers: An ultrafast and nanosecond time-resolved spectroscopic and density functional theory study
Title | Photophysics and photodeprotection reactions of p-methoxyphenacyl phototriggers: An ultrafast and nanosecond time-resolved spectroscopic and density functional theory study | ||||||||
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Authors | |||||||||
Issue Date | 2010 | ||||||||
Publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc | ||||||||
Citation | Journal Of Organic Chemistry, 2010, v. 75 n. 17, p. 5837-5851 How to Cite? | ||||||||
Abstract | Time-resolved spectroscopic experiments were performed to investigate the kinetics and mechanisms of the photodeprotection reactions for p-methoxyphenacyl (pMP) compounds, p-methoxyphenacyl diethyl phosphate (MPEP) and diphenyl phosphate (MPPP). The experimental results reveal that compared to the previous reports for the counterpart p-hydroxyphenacyl (pHP) phosphates, the 3nπ/ππ* mixed character triplet of pMP acts as a reactive precursor that leads to the subsequent solvent and leaving group dependent chemical reactions and further affects the formation of photoproducts. The MPPP triplet in H 2O/CH 3CN and in fluorinated alcohols shows a rapid heterolytic cleavage (τ ≈ 5.4 ns) that results in deprotection and formation of a solvolytic rearrangement product, whereas the MPPP triplet in CH 3CN and the MPEP triplet in CH 3CN and H 2O/CH 3CN and fluorinated alcohols decay on a much longer time scale (τ ≈ 100 ns) with little observation of the rearrangement product. The density functional theory (DFT) calculations reveal a substantial solvation effect that is connected with the methoxy versus hydroxyl substitution in accounting for the different deprotection reactivity of pMP and pHP compounds. The results reported here provide new insight in elucidating the solvent and leaving group dependent dual reactivity of pMP compounds on the formation of the rearrangement versus reductive photoproduct. © 2010 American Chemical Society. | ||||||||
Persistent Identifier | http://hdl.handle.net/10722/138996 | ||||||||
ISSN | 2023 Impact Factor: 3.3 2023 SCImago Journal Rankings: 0.724 | ||||||||
ISI Accession Number ID |
Funding Information: The research was supported by grants from the Research Grants Council of Hong Kong (HKU 1/01C and HKU 7039/07P) to D.L.P. and (PolyU/7029/07p and PolyU/5007/08p) to W.M.K. 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. | ||||||||
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Grants |
DC Field | Value | Language |
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dc.contributor.author | An, HY | en_HK |
dc.contributor.author | Kwok, WM | en_HK |
dc.contributor.author | Ma, C | en_HK |
dc.contributor.author | Guan, X | en_HK |
dc.contributor.author | Kan, JTW | en_HK |
dc.contributor.author | Toy, PH | en_HK |
dc.contributor.author | Phillips, DL | en_HK |
dc.date.accessioned | 2011-09-23T05:43:51Z | - |
dc.date.available | 2011-09-23T05:43:51Z | - |
dc.date.issued | 2010 | en_HK |
dc.identifier.citation | Journal Of Organic Chemistry, 2010, v. 75 n. 17, p. 5837-5851 | en_HK |
dc.identifier.issn | 0022-3263 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/138996 | - |
dc.description.abstract | Time-resolved spectroscopic experiments were performed to investigate the kinetics and mechanisms of the photodeprotection reactions for p-methoxyphenacyl (pMP) compounds, p-methoxyphenacyl diethyl phosphate (MPEP) and diphenyl phosphate (MPPP). The experimental results reveal that compared to the previous reports for the counterpart p-hydroxyphenacyl (pHP) phosphates, the 3nπ/ππ* mixed character triplet of pMP acts as a reactive precursor that leads to the subsequent solvent and leaving group dependent chemical reactions and further affects the formation of photoproducts. The MPPP triplet in H 2O/CH 3CN and in fluorinated alcohols shows a rapid heterolytic cleavage (τ ≈ 5.4 ns) that results in deprotection and formation of a solvolytic rearrangement product, whereas the MPPP triplet in CH 3CN and the MPEP triplet in CH 3CN and H 2O/CH 3CN and fluorinated alcohols decay on a much longer time scale (τ ≈ 100 ns) with little observation of the rearrangement product. The density functional theory (DFT) calculations reveal a substantial solvation effect that is connected with the methoxy versus hydroxyl substitution in accounting for the different deprotection reactivity of pMP and pHP compounds. The results reported here provide new insight in elucidating the solvent and leaving group dependent dual reactivity of pMP compounds on the formation of the rearrangement versus reductive photoproduct. © 2010 American Chemical Society. | en_HK |
dc.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc | en_HK |
dc.relation.ispartof | Journal of Organic Chemistry | en_HK |
dc.subject.mesh | Aldehydes - chemical synthesis - chemistry | - |
dc.subject.mesh | Computer Simulation | - |
dc.subject.mesh | Esters - chemical synthesis - chemistry | - |
dc.subject.mesh | Quantum Theory | - |
dc.subject.mesh | Spectrometry, Fluorescence | - |
dc.title | Photophysics and photodeprotection reactions of p-methoxyphenacyl phototriggers: An ultrafast and nanosecond time-resolved spectroscopic and density functional theory study | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Ma, C:macs@hkucc.hku.hk | en_HK |
dc.identifier.email | Toy, PH:phtoy@hkucc.hku.hk | en_HK |
dc.identifier.email | Phillips, DL:phillips@hku.hk | en_HK |
dc.identifier.authority | Ma, C=rp00758 | en_HK |
dc.identifier.authority | Toy, PH=rp00791 | en_HK |
dc.identifier.authority | Phillips, DL=rp00770 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1021/jo100848b | en_HK |
dc.identifier.pmid | 20684501 | - |
dc.identifier.scopus | eid_2-s2.0-77956166549 | en_HK |
dc.identifier.hkuros | 195707 | en_US |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-77956166549&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 75 | en_HK |
dc.identifier.issue | 17 | en_HK |
dc.identifier.spage | 5837 | en_HK |
dc.identifier.epage | 5851 | en_HK |
dc.identifier.isi | WOS:000281180100006 | - |
dc.publisher.place | United States | en_HK |
dc.relation.project | Ultrafast laser facility for investigations of novel electronic excited states and intermediates in inorganic photochemistry, semiconductor materials and nanomaterials | - |
dc.identifier.scopusauthorid | An, HY=54411879800 | en_HK |
dc.identifier.scopusauthorid | Kwok, WM=7103129332 | en_HK |
dc.identifier.scopusauthorid | Ma, C=7402924979 | en_HK |
dc.identifier.scopusauthorid | Guan, X=8313149700 | en_HK |
dc.identifier.scopusauthorid | Kan, JTW=8753189200 | en_HK |
dc.identifier.scopusauthorid | Toy, PH=7006579247 | en_HK |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_HK |
dc.identifier.issnl | 0022-3263 | - |