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Article: Time-resolved resonance raman and computational investigation of the influence of 4-acetamido and 4-N-methylacetamido substituents on the chemistry of phenylnitrene
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TitleTime-resolved resonance raman and computational investigation of the influence of 4-acetamido and 4-N-methylacetamido substituents on the chemistry of phenylnitrene
 
AuthorsXue, J2
Vyas, S1
Du, Y2
Luk, HL1
Chuang, YP2
But, TYS2
Toy, PH2
Wang, J1
Winter, AH1
Phillips, DL2
Hadad, CM1
Platz, MS1
 
KeywordsCas-scf
Computational investigation
Electronic configuration
Geometrical distortion
Intersystem crossing
 
Issue Date2011
 
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
 
CitationJournal Of Physical Chemistry A, 2011, v. 115 n. 26, p. 7521-7530 [How to Cite?]
DOI: http://dx.doi.org/10.1021/jp201821d
 
AbstractA time-resolved resonance Raman (TR 3) and computational investigation of the photochemistry of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide in acetonitrile is presented. Photolysis of 4-acetamidophenyl azide appears to initially produce singlet 4-acetamidophenylnitrene which undergoes fast intersystem crossing (ISC) to form triplet 4-acetamidophenylnitrene. The latter species formally produces 4,4′-bisacetamidoazobenzene. RI-CC2/TZVP and TD-B3LYP/TZVP calculations predict the formation of the singlet nitrene from the photogenerated S 1 surface of the azide excited state. The triplet 4-acetamidophenylnitrene and 4,4′-bisacetamidoazobenzene species are both clearly observed on the nanosecond to microsecond time-scale in TR 3 experiments. In contrast, only one species can be observed in analogous TR 3 experiments after photolysis of 4-N-methylacetamidophenyl azide in acetonitrile, and this species is tentatively assigned to the compound resulting from dimerization of a 1,2-didehydroazepine. The different photochemical reaction outcomes for the photolysis of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide molecules indicate that the 4-acetamido group has a substantial influence on the ISC rate of the corresponding substituted singlet phenylnitrene, but the 4-N-methylacetamido group does not. CASSCF analyses predict that both singlet nitrenes have open-shell electronic configurations and concluded that the dissimilarity in the photochemistry is probably due to differential geometrical distortions between the states. We briefly discuss the probable implications of this intriguing substitution effect on the photochemistry of phenyl azides and the chemistry of the related nitrenes. © 2011 American Chemical Society.
 
ISSN1089-5639
2013 Impact Factor: 2.775
 
DOIhttp://dx.doi.org/10.1021/jp201821d
 
ISI Accession Number IDWOS:000292281300015
Funding AgencyGrant Number
Research Grants Council (RGC) of Hong KongHKU-7039/07P
US National Science FoundationCHE-0743258
OSU
Funding Information:

This work was supported by grants from the Research Grants Council (RGC) of Hong Kong (HKU-7039/07P) to D.L.P., while C.M.H. and M.S.P. acknowledge financial support of this work by the US National Science Foundation (CHE-0743258). Generous computational resourced from the Ohio Supercomputer Center is also gratefully acknowledged. S.V. acknowledges the OSU University Presidential Fellowship.

 
ReferencesReferences in Scopus
 
DC FieldValue
dc.contributor.authorXue, J
 
dc.contributor.authorVyas, S
 
dc.contributor.authorDu, Y
 
dc.contributor.authorLuk, HL
 
dc.contributor.authorChuang, YP
 
dc.contributor.authorBut, TYS
 
dc.contributor.authorToy, PH
 
dc.contributor.authorWang, J
 
dc.contributor.authorWinter, AH
 
dc.contributor.authorPhillips, DL
 
dc.contributor.authorHadad, CM
 
dc.contributor.authorPlatz, MS
 
dc.date.accessioned2011-09-23T05:43:46Z
 
dc.date.available2011-09-23T05:43:46Z
 
dc.date.issued2011
 
dc.description.abstractA time-resolved resonance Raman (TR 3) and computational investigation of the photochemistry of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide in acetonitrile is presented. Photolysis of 4-acetamidophenyl azide appears to initially produce singlet 4-acetamidophenylnitrene which undergoes fast intersystem crossing (ISC) to form triplet 4-acetamidophenylnitrene. The latter species formally produces 4,4′-bisacetamidoazobenzene. RI-CC2/TZVP and TD-B3LYP/TZVP calculations predict the formation of the singlet nitrene from the photogenerated S 1 surface of the azide excited state. The triplet 4-acetamidophenylnitrene and 4,4′-bisacetamidoazobenzene species are both clearly observed on the nanosecond to microsecond time-scale in TR 3 experiments. In contrast, only one species can be observed in analogous TR 3 experiments after photolysis of 4-N-methylacetamidophenyl azide in acetonitrile, and this species is tentatively assigned to the compound resulting from dimerization of a 1,2-didehydroazepine. The different photochemical reaction outcomes for the photolysis of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide molecules indicate that the 4-acetamido group has a substantial influence on the ISC rate of the corresponding substituted singlet phenylnitrene, but the 4-N-methylacetamido group does not. CASSCF analyses predict that both singlet nitrenes have open-shell electronic configurations and concluded that the dissimilarity in the photochemistry is probably due to differential geometrical distortions between the states. We briefly discuss the probable implications of this intriguing substitution effect on the photochemistry of phenyl azides and the chemistry of the related nitrenes. © 2011 American Chemical Society.
 
dc.description.natureLink_to_subscribed_fulltext
 
dc.identifier.citationJournal Of Physical Chemistry A, 2011, v. 115 n. 26, p. 7521-7530 [How to Cite?]
DOI: http://dx.doi.org/10.1021/jp201821d
 
dc.identifier.doihttp://dx.doi.org/10.1021/jp201821d
 
dc.identifier.epage7530
 
dc.identifier.hkuros194600
 
dc.identifier.isiWOS:000292281300015
Funding AgencyGrant Number
Research Grants Council (RGC) of Hong KongHKU-7039/07P
US National Science FoundationCHE-0743258
OSU
Funding Information:

This work was supported by grants from the Research Grants Council (RGC) of Hong Kong (HKU-7039/07P) to D.L.P., while C.M.H. and M.S.P. acknowledge financial support of this work by the US National Science Foundation (CHE-0743258). Generous computational resourced from the Ohio Supercomputer Center is also gratefully acknowledged. S.V. acknowledges the OSU University Presidential Fellowship.

 
dc.identifier.issn1089-5639
2013 Impact Factor: 2.775
 
dc.identifier.issue26
 
dc.identifier.pmid21648388
 
dc.identifier.scopuseid_2-s2.0-79959798177
 
dc.identifier.spage7521
 
dc.identifier.urihttp://hdl.handle.net/10722/138990
 
dc.identifier.volume115
 
dc.languageeng
 
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
 
dc.publisher.placeUnited States
 
dc.relation.ispartofJournal of Physical Chemistry A
 
dc.relation.referencesReferences in Scopus
 
dc.subjectCas-scf
 
dc.subjectComputational investigation
 
dc.subjectElectronic configuration
 
dc.subjectGeometrical distortion
 
dc.subjectIntersystem crossing
 
dc.titleTime-resolved resonance raman and computational investigation of the influence of 4-acetamido and 4-N-methylacetamido substituents on the chemistry of phenylnitrene
 
dc.typeArticle
 
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<description.abstract>A time-resolved resonance Raman (TR 3) and computational investigation of the photochemistry of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide in acetonitrile is presented. Photolysis of 4-acetamidophenyl azide appears to initially produce singlet 4-acetamidophenylnitrene which undergoes fast intersystem crossing (ISC) to form triplet 4-acetamidophenylnitrene. The latter species formally produces 4,4&#8242;-bisacetamidoazobenzene. RI-CC2/TZVP and TD-B3LYP/TZVP calculations predict the formation of the singlet nitrene from the photogenerated S 1 surface of the azide excited state. The triplet 4-acetamidophenylnitrene and 4,4&#8242;-bisacetamidoazobenzene species are both clearly observed on the nanosecond to microsecond time-scale in TR 3 experiments. In contrast, only one species can be observed in analogous TR 3 experiments after photolysis of 4-N-methylacetamidophenyl azide in acetonitrile, and this species is tentatively assigned to the compound resulting from dimerization of a 1,2-didehydroazepine. The different photochemical reaction outcomes for the photolysis of 4-acetamidophenyl azide and 4-N-methylacetamidophenyl azide molecules indicate that the 4-acetamido group has a substantial influence on the ISC rate of the corresponding substituted singlet phenylnitrene, but the 4-N-methylacetamido group does not. CASSCF analyses predict that both singlet nitrenes have open-shell electronic configurations and concluded that the dissimilarity in the photochemistry is probably due to differential geometrical distortions between the states. We briefly discuss the probable implications of this intriguing substitution effect on the photochemistry of phenyl azides and the chemistry of the related nitrenes. &#169; 2011 American Chemical Society.</description.abstract>
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Author Affiliations
  1. Ohio State University
  2. The University of Hong Kong