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Article: Organic triplet emissions of arylacetylide moieties harnessed through coordination to [Au(PCy 3)] +. Effect of molecular structure upon photoluminescent properties

TitleOrganic triplet emissions of arylacetylide moieties harnessed through coordination to [Au(PCy 3)] +. Effect of molecular structure upon photoluminescent properties
Authors
Issue Date2002
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2002, v. 124 n. 49, p. 14696-14706 How to Cite?
AbstractA family of mono- and binuclear Cy 3P-supported gold(I) complexes containing various π-conjugated linear arylacetylide ligands, including the two homologous series (Cy 3P)Au(C≡CC 6H 4) n-1 (C≡CPh) and (Cy 3P)Au(C≡CC 6H 4) n C≡C≡Au(PCy 3) (n = 1-4), have been prepared. X-ray crystal analyses revealed no intermolecular aurophilic interactions in their crystal lattice. The lowest-energy singlet transitions are predominately intraligand in nature and exhibit both phenyl and acetylenic 1(ππ*) character. Strong photoluminescence is detected in solid and solution states under ambient conditions, with lifetimes in the microsecond regime. For complexes with a single arylacetylide group, only phosphorescence from the arylacetylide 3(ππ*) state is observed. Vibrational spacings in the solid-state emission spectra can be attributed to a combination of phenyl ring deformation and symmetric phenyl ring and C≡C stretches. Additional delayed-fluorescence emission is recorded for complexes with multiple p-arylacetylide units, and this is attributed to a triplet-triplet annihilation process. The phosphorescence energy of these complexes are readily modified by altering the length of the conjugated arylacetylide system, while the intensity of phosphorescence relative to fluorescence decreases when the p-arylacetylide chain is elongated. Information regarding the nature and relative energies of arylacetylide singlet and triplet excited states has been derived from the two homologous series and extrapolated to polymeric arylacetylide species. The 3(ππ*) excited-state reduction potentials E° [Au +/Au*] (Au = 1a, 2, and 4) are estimated to be -1.80, -1.28, and -1.17 V versus SSCE, respectively.
Persistent Identifierhttp://hdl.handle.net/10722/167751
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChao, HYen_HK
dc.contributor.authorLu, Wen_HK
dc.contributor.authorLi, Yen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-10-08T03:10:59Z-
dc.date.available2012-10-08T03:10:59Z-
dc.date.issued2002en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2002, v. 124 n. 49, p. 14696-14706en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167751-
dc.description.abstractA family of mono- and binuclear Cy 3P-supported gold(I) complexes containing various π-conjugated linear arylacetylide ligands, including the two homologous series (Cy 3P)Au(C≡CC 6H 4) n-1 (C≡CPh) and (Cy 3P)Au(C≡CC 6H 4) n C≡C≡Au(PCy 3) (n = 1-4), have been prepared. X-ray crystal analyses revealed no intermolecular aurophilic interactions in their crystal lattice. The lowest-energy singlet transitions are predominately intraligand in nature and exhibit both phenyl and acetylenic 1(ππ*) character. Strong photoluminescence is detected in solid and solution states under ambient conditions, with lifetimes in the microsecond regime. For complexes with a single arylacetylide group, only phosphorescence from the arylacetylide 3(ππ*) state is observed. Vibrational spacings in the solid-state emission spectra can be attributed to a combination of phenyl ring deformation and symmetric phenyl ring and C≡C stretches. Additional delayed-fluorescence emission is recorded for complexes with multiple p-arylacetylide units, and this is attributed to a triplet-triplet annihilation process. The phosphorescence energy of these complexes are readily modified by altering the length of the conjugated arylacetylide system, while the intensity of phosphorescence relative to fluorescence decreases when the p-arylacetylide chain is elongated. Information regarding the nature and relative energies of arylacetylide singlet and triplet excited states has been derived from the two homologous series and extrapolated to polymeric arylacetylide species. The 3(ππ*) excited-state reduction potentials E° [Au +/Au*] (Au = 1a, 2, and 4) are estimated to be -1.80, -1.28, and -1.17 V versus SSCE, respectively.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titleOrganic triplet emissions of arylacetylide moieties harnessed through coordination to [Au(PCy 3)] +. Effect of molecular structure upon photoluminescent propertiesen_HK
dc.typeArticleen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja0209417en_HK
dc.identifier.pmid12465981-
dc.identifier.scopuseid_2-s2.0-0037065288en_HK
dc.identifier.hkuros83810-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037065288&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume124en_HK
dc.identifier.issue49en_HK
dc.identifier.spage14696en_HK
dc.identifier.epage14706en_HK
dc.identifier.isiWOS:000179661000042-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChao, HY=7202973715en_HK
dc.identifier.scopusauthoridLu, W=55277832700en_HK
dc.identifier.scopusauthoridLi, Y=40861370300en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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