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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

TitleTime-resolved resonance raman and computational investigation of the influence of 4-acetamido and 4-N-methylacetamido substituents on the chemistry of phenylnitrene
Authors
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
Citation
Journal Of Physical Chemistry A, 2011, v. 115 n. 26, p. 7521-7530 How to Cite?
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′-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.
Persistent Identifierhttp://hdl.handle.net/10722/138990
ISSN
2013 Impact Factor: 2.775
ISI Accession Number ID
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.

References

 

Author Affiliations
  1. Ohio State University
  2. The University of Hong Kong
DC FieldValueLanguage
dc.contributor.authorXue, Jen_HK
dc.contributor.authorVyas, Sen_HK
dc.contributor.authorDu, Yen_HK
dc.contributor.authorLuk, HLen_HK
dc.contributor.authorChuang, YPen_HK
dc.contributor.authorBut, TYSen_HK
dc.contributor.authorToy, PHen_HK
dc.contributor.authorWang, Jen_HK
dc.contributor.authorWinter, AHen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorHadad, CMen_HK
dc.contributor.authorPlatz, MSen_HK
dc.date.accessioned2011-09-23T05:43:46Z-
dc.date.available2011-09-23T05:43:46Z-
dc.date.issued2011en_HK
dc.identifier.citationJournal Of Physical Chemistry A, 2011, v. 115 n. 26, p. 7521-7530en_HK
dc.identifier.issn1089-5639en_HK
dc.identifier.urihttp://hdl.handle.net/10722/138990-
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.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_HK
dc.relation.ispartofJournal of Physical Chemistry Aen_HK
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 phenylnitreneen_HK
dc.typeArticleen_HK
dc.identifier.emailToy, PH:phtoy@hkucc.hku.hken_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityToy, PH=rp00791en_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jp201821den_HK
dc.identifier.pmid21648388-
dc.identifier.scopuseid_2-s2.0-79959798177en_HK
dc.identifier.hkuros194600en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-79959798177&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume115en_HK
dc.identifier.issue26en_HK
dc.identifier.spage7521en_HK
dc.identifier.epage7530en_HK
dc.identifier.isiWOS:000292281300015-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridXue, J=23007272500en_HK
dc.identifier.scopusauthoridVyas, S=7101837857en_HK
dc.identifier.scopusauthoridDu, Y=35310175500en_HK
dc.identifier.scopusauthoridLuk, HL=35189439100en_HK
dc.identifier.scopusauthoridChuang, YP=23670354300en_HK
dc.identifier.scopusauthoridBut, TYS=8774303500en_HK
dc.identifier.scopusauthoridToy, PH=7006579247en_HK
dc.identifier.scopusauthoridWang, J=36100585800en_HK
dc.identifier.scopusauthoridWinter, AH=7202642455en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridHadad, CM=7005455605en_HK
dc.identifier.scopusauthoridPlatz, MS=7004584689en_HK

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