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Article: Tuning from π,π* to charge-transfer excited states in styryl-substituted terthiophenes: An ultrafast and steady-state emission study

TitleTuning from π,π* to charge-transfer excited states in styryl-substituted terthiophenes: An ultrafast and steady-state emission study
Authors
Issue Date2006
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
Citation
Journal Of Physical Chemistry A, 2006, v. 110 n. 24, p. 7696-7702 How to Cite?
AbstractThe steady-state and transient emission properties of unsubstituted terthiophene and a series of 3′-[E-2-(4-R-phenyl)ethenyl]-2,2′: 5′,2″-terthiophenes (where R = H, MeO, NH2, CN, NMe 2, NO2) have been examined. The R = NO2 compound is nonemissive at room temperature in all solvents but cyclohexane. All of the other compounds show measurable steady-state emission in a variety of solvents. The behavior of these spectra may be split into two groups. The first group, those substituted compounds with R = CN, NH2 and NMe 2, show solvatochromic behavior, where their Lippert-Mataga plots suggest changes in dipole upon photo-excitation ranging from 12.5 to 16.0 D. For the second group, where R = H and MeO (and unsubstituted terthiophene as well), the Lippert-Mataga plots indicate dipole moment changes ranging from 0 to 7.9 D. The difference in behavior between the two groups of emissive compounds can be attributed to a charge-transfer character of the emitting state in the first group. This conclusion is supported by density functional theory calculations, which show that the frontier MOs in the group one compounds are spatially separated whereas those of group two have frontier MOs that are delocalized over both the styryl and terthiophene moieties. Picosecond time-resolved fluorescence spectroscopy reveals that unsubstituted terthiophene has the shortest emission lifetime of 140 ps in acetonitrile. For the styryl substituted terthiophenes, the lifetimes are much longer and range from 320 to 670 ps for R = CN and NMe2 respectively, a result that can be explained in terms of a smaller rate of intersystem crossing in these compounds. © 2006 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168028
ISSN
2015 Impact Factor: 2.883
2015 SCImago Journal Rankings: 1.231
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorClarke, TMen_US
dc.contributor.authorGordon, KCen_US
dc.contributor.authorKwok, WMen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorOfficer, DLen_US
dc.date.accessioned2012-10-08T03:14:20Z-
dc.date.available2012-10-08T03:14:20Z-
dc.date.issued2006en_US
dc.identifier.citationJournal Of Physical Chemistry A, 2006, v. 110 n. 24, p. 7696-7702en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/10722/168028-
dc.description.abstractThe steady-state and transient emission properties of unsubstituted terthiophene and a series of 3′-[E-2-(4-R-phenyl)ethenyl]-2,2′: 5′,2″-terthiophenes (where R = H, MeO, NH2, CN, NMe 2, NO2) have been examined. The R = NO2 compound is nonemissive at room temperature in all solvents but cyclohexane. All of the other compounds show measurable steady-state emission in a variety of solvents. The behavior of these spectra may be split into two groups. The first group, those substituted compounds with R = CN, NH2 and NMe 2, show solvatochromic behavior, where their Lippert-Mataga plots suggest changes in dipole upon photo-excitation ranging from 12.5 to 16.0 D. For the second group, where R = H and MeO (and unsubstituted terthiophene as well), the Lippert-Mataga plots indicate dipole moment changes ranging from 0 to 7.9 D. The difference in behavior between the two groups of emissive compounds can be attributed to a charge-transfer character of the emitting state in the first group. This conclusion is supported by density functional theory calculations, which show that the frontier MOs in the group one compounds are spatially separated whereas those of group two have frontier MOs that are delocalized over both the styryl and terthiophene moieties. Picosecond time-resolved fluorescence spectroscopy reveals that unsubstituted terthiophene has the shortest emission lifetime of 140 ps in acetonitrile. For the styryl substituted terthiophenes, the lifetimes are much longer and range from 320 to 670 ps for R = CN and NMe2 respectively, a result that can be explained in terms of a smaller rate of intersystem crossing in these compounds. © 2006 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_US
dc.relation.ispartofJournal of Physical Chemistry Aen_US
dc.titleTuning from π,π* to charge-transfer excited states in styryl-substituted terthiophenes: An ultrafast and steady-state emission studyen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jp0600312en_US
dc.identifier.pmid16774217-
dc.identifier.scopuseid_2-s2.0-33745767306en_US
dc.identifier.hkuros117606-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33745767306&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume110en_US
dc.identifier.issue24en_US
dc.identifier.spage7696en_US
dc.identifier.epage7702en_US
dc.identifier.isiWOS:000238284400027-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridClarke, TM=7202914994en_US
dc.identifier.scopusauthoridGordon, KC=7202357498en_US
dc.identifier.scopusauthoridKwok, WM=7103129332en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridOfficer, DL=6603900312en_US

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