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Article: Raman spectroscopy of short-lived terthiophene radical cations generated by photochemical and chemical oxidation

TitleRaman spectroscopy of short-lived terthiophene radical cations generated by photochemical and chemical oxidation
Authors
KeywordsDensity functional calculations
Electron transfer
Laser spectroscopy
Radical ions
Raman spectroscopy
Issue Date2006
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.chemphyschem.com
Citation
Chemphyschem, 2006, v. 7 n. 6, p. 1276-1285 How to Cite?
AbstractThe Raman spectra of various terthiophene radical cations are investigated; namely those of unsubstituted terthiophene and two styryl-substituted terthiophenes. Transient pump-probe resonance Raman spectroscopy is used to measure the short-lived radical cation spectra of non-end-capped 2,2′:5′,2″-terthiophene (3T) and 3′-[(E)-2-(4- nitrophenyl)ethenyl]-2,2′:5′,2″-terthiophene (NO 2-pe3T). For these two compounds, the radical cations are generated via either direct photogeneration or photochemically using the electron acceptor tetracyanoethylene. The radical cation of 5,5″-dimethyl-3′-[(E)-2- phenylethenyl]-2,2′:5′,2″-terthiophene (DM-pe3T) is stable for up to five minutes as a result of the two a end caps and continuous-wave resonance Raman spectroscopy and chemical oxidation is used to obtain the spectrum of this radical cation. The resonance Raman spectra of all three terthiophene radical cations are dominated by a group of very intense bands in the low-frequency region. These bands have been assigned, by density functional theory methods, to C-S stretching modes coupled to thiophene ring deformations. These modes are significantly less intense in the σ-dimer of NO 2-pe3T [i.e. the corresponding styryl sexithiophene (NO 2-pe3T)2]. This observation is attributed to a smaller change in the C-S bond order in the sexithiophene compared to the analogous terthiophene. This bond order difference may be rationalised by consideration of the singly occupied molecular orbital and lowest unoccupied molecular orbital, which are involved in the electronic transition probed by the laser excitation wavelength. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/68772
ISSN
2015 Impact Factor: 3.138
2015 SCImago Journal Rankings: 1.385
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorClarke, TMen_HK
dc.contributor.authorGordon, KCen_HK
dc.contributor.authorWing, SCen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorWagner, Pen_HK
dc.contributor.authorOfficer, DLen_HK
dc.date.accessioned2010-09-06T06:07:35Z-
dc.date.available2010-09-06T06:07:35Z-
dc.date.issued2006en_HK
dc.identifier.citationChemphyschem, 2006, v. 7 n. 6, p. 1276-1285en_HK
dc.identifier.issn1439-4235en_HK
dc.identifier.urihttp://hdl.handle.net/10722/68772-
dc.description.abstractThe Raman spectra of various terthiophene radical cations are investigated; namely those of unsubstituted terthiophene and two styryl-substituted terthiophenes. Transient pump-probe resonance Raman spectroscopy is used to measure the short-lived radical cation spectra of non-end-capped 2,2′:5′,2″-terthiophene (3T) and 3′-[(E)-2-(4- nitrophenyl)ethenyl]-2,2′:5′,2″-terthiophene (NO 2-pe3T). For these two compounds, the radical cations are generated via either direct photogeneration or photochemically using the electron acceptor tetracyanoethylene. The radical cation of 5,5″-dimethyl-3′-[(E)-2- phenylethenyl]-2,2′:5′,2″-terthiophene (DM-pe3T) is stable for up to five minutes as a result of the two a end caps and continuous-wave resonance Raman spectroscopy and chemical oxidation is used to obtain the spectrum of this radical cation. The resonance Raman spectra of all three terthiophene radical cations are dominated by a group of very intense bands in the low-frequency region. These bands have been assigned, by density functional theory methods, to C-S stretching modes coupled to thiophene ring deformations. These modes are significantly less intense in the σ-dimer of NO 2-pe3T [i.e. the corresponding styryl sexithiophene (NO 2-pe3T)2]. This observation is attributed to a smaller change in the C-S bond order in the sexithiophene compared to the analogous terthiophene. This bond order difference may be rationalised by consideration of the singly occupied molecular orbital and lowest unoccupied molecular orbital, which are involved in the electronic transition probed by the laser excitation wavelength. © 2006 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.chemphyschem.comen_HK
dc.relation.ispartofChemPhysChemen_HK
dc.subjectDensity functional calculationsen_HK
dc.subjectElectron transferen_HK
dc.subjectLaser spectroscopyen_HK
dc.subjectRadical ionsen_HK
dc.subjectRaman spectroscopyen_HK
dc.titleRaman spectroscopy of short-lived terthiophene radical cations generated by photochemical and chemical oxidationen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1439-4235&volume=7&spage=12476&epage=1285&date=2006&atitle=Raman+spectroscopy+of+short-lived+terthiophene+radical+cations+generated+by+photochemical+and+chemical+oxidationen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/cphc.200500680en_HK
dc.identifier.scopuseid_2-s2.0-33745428741en_HK
dc.identifier.hkuros119102en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33745428741&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume7en_HK
dc.identifier.issue6en_HK
dc.identifier.spage1276en_HK
dc.identifier.epage1285en_HK
dc.identifier.isiWOS:000238415400017-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridClarke, TM=7202914994en_HK
dc.identifier.scopusauthoridGordon, KC=7202357498en_HK
dc.identifier.scopusauthoridWing, SC=8761955400en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridWagner, P=7402964003en_HK
dc.identifier.scopusauthoridOfficer, DL=6603900312en_HK

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