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Article: Organic triplet excited states of gold(I) complexes with oligo(o- or m-phenyleneethynylene) ligands: conjunction of steady-state and time-resolved spectroscopic studies on exciton delocalization and emission pathways

TitleOrganic triplet excited states of gold(I) complexes with oligo(o- or m-phenyleneethynylene) ligands: conjunction of steady-state and time-resolved spectroscopic studies on exciton delocalization and emission pathways
Authors
Issue Date2011
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, 2011, v. 133 n. 35, p. 14120-14135 How to Cite?
AbstractA series of mononuclear and binuclear gold(I) complexes containing oligo(o- or m-phenyleneethynylene) (PE) ligands, namely [PhC identical withC(C(6)H(4)-1,2-C identical withC)(n-1)Au(PCy(3))] (n = 2-4, 4a-c), [mu-{C identical withC-(1,2-C(6)H(4)C identical withC)(n)}{Au(PCy(3))}(2)] (n = 1-6, 8, 5a-g), [PhC identical withC(C(6)H(4)-1,3-C identical withC)(n-1)Au(PCy(3))] (n = 2-4, 6a-c), and [mu-{C identical withC-(1,3-C(6)H(4)C identical withC)(n)}{Au(PCy(3))}(2)] (n = 1, 2, 7a,b), were synthesized and structurally characterized. Extensive spectroscopic measurements have been performed by applying combined methods of femtosecond transient absorption (fs-TA), fs time-resolved fluorescence (fs-TRF), and nanosecond time-resolved emission (ns-TRE) coupled with steady-state absorption and emission spectroscopy at both ambient and low (77 K) temperatures to directly probe the temporal evolution of the excited states and to determine the dynamics and spectral signatures for the involved singlet (S(1)) and triplet (T(1)) excited states. The results reveal that S(1) and T(1) both feature ligand-centered electronic transitions with pipi* character associated with the phenyl and acetylene moieties. The (3)pipi* emission of the PE ligands is switched on by the attachment of [Au(PCy(3))](+) fragment(s) due to the heavy-atom effect. T(1)((3)pipi*) was found to form with nearly unity efficiency through intersystem crossing (ISC) from S(1)((1)pipi*). The ISC time constants were determined to be approximately 50, 35, and 40 ps for 4b and 6a,b, respectively. Dual emission composed of fluorescence from S(1) and phosphorescence from T(1) were observed for most of the complexes except 5a and 7a, where only phosphorescence was found. The fluorescence at ambient temperature is accounted for by both the short-lived prompt fluorescence (PF) and long-lived delayed fluorescence (DF, lifetime on microsecond time scale). Explicit evidence was presented for a triplet-triplet annihilation mechanism for the generation of DF. Ligand length and substitution-dependent dynamics of T(1) are the key factors governing the dual emission character of the complexes. By extrapolation from the plot of emission energy against the PE chain length of the [Au(PCy(3))](+) complexes with oligo(o-PE) or oligo(m-PE) ligands, the triplet emission energies were estimated to be approximately 530 and approximately 470 nm for poly(o-PE) and poly(m-PE), respectively. Additionally, we assign the unusual red shifts of 983 cm(-1) from [PhC identical withCAu(PCy(3))] (1) to [mu-{1,3-(C identical withC)(2)C(6)H(4)}{Au(PCy(3))}(2)] (7a) and 462 cm(-1) from 7a to [mu(3)-{1,3,5-(C identical withC)(3)C(6)H(3)}{Au(PCy(3))}(3)] (8) in the phosphorescence energies to excitonic coupling interactions between the C identical withCAu(PCy(3)) arms in the triplet excited states. These complexes, together with those previously reported [Au(PCy(3))](+) complexes containing oligo(p-PE) ligands ( J. Am. Chem. Soc. 2002 , 124 , 14696 - 14706 ), form a collection of oligo(phenyleneethynylene) complexes exhibiting organic triplet emission in solution under ambient conditions. The remarkable feature of these complexes in exhibiting TTA prompted DF in conjunction with high formation efficiency of T(1)((3)pipi*) affords an opportunity for emission spectra to cover a wide range of wavelengths. This may have implication in the development of PE-based molecular materials for future optical applications.
Persistent Identifierhttp://hdl.handle.net/10722/159411
ISSN
2014 Impact Factor: 12.113
2014 SCImago Journal Rankings: 5.567
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLu, Wen_US
dc.contributor.authorKwok, WMen_US
dc.contributor.authorMa, Cen_US
dc.contributor.authorChan, CTLen_US
dc.contributor.authorZhu, MXen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-08-16T05:49:10Z-
dc.date.available2012-08-16T05:49:10Z-
dc.date.issued2011en_US
dc.identifier.citationJournal of the American Chemical Society, 2011, v. 133 n. 35, p. 14120-14135en_US
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/159411-
dc.description.abstractA series of mononuclear and binuclear gold(I) complexes containing oligo(o- or m-phenyleneethynylene) (PE) ligands, namely [PhC identical withC(C(6)H(4)-1,2-C identical withC)(n-1)Au(PCy(3))] (n = 2-4, 4a-c), [mu-{C identical withC-(1,2-C(6)H(4)C identical withC)(n)}{Au(PCy(3))}(2)] (n = 1-6, 8, 5a-g), [PhC identical withC(C(6)H(4)-1,3-C identical withC)(n-1)Au(PCy(3))] (n = 2-4, 6a-c), and [mu-{C identical withC-(1,3-C(6)H(4)C identical withC)(n)}{Au(PCy(3))}(2)] (n = 1, 2, 7a,b), were synthesized and structurally characterized. Extensive spectroscopic measurements have been performed by applying combined methods of femtosecond transient absorption (fs-TA), fs time-resolved fluorescence (fs-TRF), and nanosecond time-resolved emission (ns-TRE) coupled with steady-state absorption and emission spectroscopy at both ambient and low (77 K) temperatures to directly probe the temporal evolution of the excited states and to determine the dynamics and spectral signatures for the involved singlet (S(1)) and triplet (T(1)) excited states. The results reveal that S(1) and T(1) both feature ligand-centered electronic transitions with pipi* character associated with the phenyl and acetylene moieties. The (3)pipi* emission of the PE ligands is switched on by the attachment of [Au(PCy(3))](+) fragment(s) due to the heavy-atom effect. T(1)((3)pipi*) was found to form with nearly unity efficiency through intersystem crossing (ISC) from S(1)((1)pipi*). The ISC time constants were determined to be approximately 50, 35, and 40 ps for 4b and 6a,b, respectively. Dual emission composed of fluorescence from S(1) and phosphorescence from T(1) were observed for most of the complexes except 5a and 7a, where only phosphorescence was found. The fluorescence at ambient temperature is accounted for by both the short-lived prompt fluorescence (PF) and long-lived delayed fluorescence (DF, lifetime on microsecond time scale). Explicit evidence was presented for a triplet-triplet annihilation mechanism for the generation of DF. Ligand length and substitution-dependent dynamics of T(1) are the key factors governing the dual emission character of the complexes. By extrapolation from the plot of emission energy against the PE chain length of the [Au(PCy(3))](+) complexes with oligo(o-PE) or oligo(m-PE) ligands, the triplet emission energies were estimated to be approximately 530 and approximately 470 nm for poly(o-PE) and poly(m-PE), respectively. Additionally, we assign the unusual red shifts of 983 cm(-1) from [PhC identical withCAu(PCy(3))] (1) to [mu-{1,3-(C identical withC)(2)C(6)H(4)}{Au(PCy(3))}(2)] (7a) and 462 cm(-1) from 7a to [mu(3)-{1,3,5-(C identical withC)(3)C(6)H(3)}{Au(PCy(3))}(3)] (8) in the phosphorescence energies to excitonic coupling interactions between the C identical withCAu(PCy(3)) arms in the triplet excited states. These complexes, together with those previously reported [Au(PCy(3))](+) complexes containing oligo(p-PE) ligands ( J. Am. Chem. Soc. 2002 , 124 , 14696 - 14706 ), form a collection of oligo(phenyleneethynylene) complexes exhibiting organic triplet emission in solution under ambient conditions. The remarkable feature of these complexes in exhibiting TTA prompted DF in conjunction with high formation efficiency of T(1)((3)pipi*) affords an opportunity for emission spectra to cover a wide range of wavelengths. This may have implication in the development of PE-based molecular materials for future optical applications.-
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html-
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.titleOrganic triplet excited states of gold(I) complexes with oligo(o- or m-phenyleneethynylene) ligands: conjunction of steady-state and time-resolved spectroscopic studies on exciton delocalization and emission pathwaysen_US
dc.typeArticleen_US
dc.identifier.emailLu, W: luwei@hku.hken_US
dc.identifier.emailMa, C: macs@hkucc.hku.hken_US
dc.identifier.emailZhu, MX: zhumingxin@hkusua.hku.hken_US
dc.identifier.emailChe, CM: cmche@hku.hken_US
dc.identifier.authorityLu, W=rp00754en_US
dc.identifier.authorityMa, C=rp00758en_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja205831v-
dc.identifier.pmid21846130-
dc.identifier.scopuseid_2-s2.0-80052326952-
dc.identifier.hkuros205442en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-80052326952&selection=ref&src=s&origin=recordpage-
dc.identifier.volume133en_US
dc.identifier.issue35-
dc.identifier.spage14120en_US
dc.identifier.epage14135en_US
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000295241400066-
dc.publisher.placeUnited States-
dc.identifier.scopusauthoridLu, W=36077781100-
dc.identifier.scopusauthoridKwok, WM=7103129332-
dc.identifier.scopusauthoridMa, C=7402924979-
dc.identifier.scopusauthoridChan, CTL=39960952700-
dc.identifier.scopusauthoridZhu, MX=51261522300-
dc.identifier.scopusauthoridChe, CM=7102442791-

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