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Article: A class of luminescent cyclometalated alkynylgold(III) complexes: synthesis, characterization, and electrochemical, photophysical, and computational studies of [Au(C^N^C)(C≡C-R)] (C^N^C = κ(3)C,N,C bis-cyclometalated 2,6-diphenylpyridyl)

TitleA class of luminescent cyclometalated alkynylgold(III) complexes: synthesis, characterization, and electrochemical, photophysical, and computational studies of [Au(C^N^C)(C≡C-R)] (C^N^C = κ(3)C,N,C bis-cyclometalated 2,6-diphenylpyridyl)
Authors
KeywordsLigand centered reduction
Oxidation wave
Photophysical
X ray crystal structures
Complexation
Issue Date2007
PublisherAmerican Chemical Society.
Citation
Journal of the American Chemical Society, 2007, v. 129 n. 14, p. 4350-4365 How to Cite?
AbstractA new class of luminescent cyclometalated alkynylgold(III) complexes, [Au(RC^N(R')^CR)(C≡CR'')], i.e., [Au(C^N^C)(C≡CR'')] (HC^N^CH = 2,6-diphenylpyridine) R'' = C6H5 1, C6H4-Cl-p 2, C6H4-NO2-p 3, C6H4-OCH3-p 4, C6H4-NH2-p 5, C6H4-C6H13-p 6, C6H13 7, [Au(tBuC^N^CtBu)(C≡CC6H5)] 8 (HtBuC^N^CtBuH = 2,6-bis(4-tert-butylphenyl)pyridine), and [Au(C^NTol^C)(C≡CC6H4-C6H13-p)] 9 (HC^NTol^CH = 2,6-diphenyl-4-p-tolylpyridine), have been synthesized and characterized. The X-ray crystal structures of most of the complexes have also been determined. Electrochemical studies show that, in general, the first oxidation wave is an alkynyl ligand-centered oxidation, while the first reduction couple is ascribed to a ligand-centered reduction of the cyclometalated ligand with the exception of 3 in which the first reduction couple is assigned as an alkynyl ligand-centered reduction. Their electronic absorption and luminescence behaviors have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the π-π* intraligand (IL) transition of the cyclometalated RC^N(R')^CR ligand with some mixing of a [π(C≡CR'') -> π*(RC^N(R')^CR)] ligand-to-ligand charge transfer (LLCT) character. The low-energy emission bands of all the complexes, with the exception of 5, are ascribed to origins mainly derived from the π-π* IL transition of the cyclometalated RC^N(R')^CR ligand. In the case of 5 that contains an electron-rich amino substituent on the alkynyl ligand, the low-energy emission band was found to show an obvious shift to the red. A change in the origin of emission is evident, and the emission of 5 is tentatively ascribed to a [π(C≡CC6H4NH2) -> π*(C^N^C)] LLCT excited-state origin. DFT and TDDFT computational studies have been performed to verify and elucidate the results of the electrochemical and photophysical studies.
Persistent Identifierhttp://hdl.handle.net/10722/69118
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References
Errata

 

DC FieldValueLanguage
dc.contributor.authorWong, KMCen_HK
dc.contributor.authorHung, LLen_HK
dc.contributor.authorLam, WHen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorYam, VWWen_HK
dc.date.accessioned2010-09-06T06:10:44Z-
dc.date.available2010-09-06T06:10:44Z-
dc.date.issued2007en_HK
dc.identifier.citationJournal of the American Chemical Society, 2007, v. 129 n. 14, p. 4350-4365en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69118-
dc.description.abstractA new class of luminescent cyclometalated alkynylgold(III) complexes, [Au(RC^N(R')^CR)(C≡CR'')], i.e., [Au(C^N^C)(C≡CR'')] (HC^N^CH = 2,6-diphenylpyridine) R'' = C6H5 1, C6H4-Cl-p 2, C6H4-NO2-p 3, C6H4-OCH3-p 4, C6H4-NH2-p 5, C6H4-C6H13-p 6, C6H13 7, [Au(tBuC^N^CtBu)(C≡CC6H5)] 8 (HtBuC^N^CtBuH = 2,6-bis(4-tert-butylphenyl)pyridine), and [Au(C^NTol^C)(C≡CC6H4-C6H13-p)] 9 (HC^NTol^CH = 2,6-diphenyl-4-p-tolylpyridine), have been synthesized and characterized. The X-ray crystal structures of most of the complexes have also been determined. Electrochemical studies show that, in general, the first oxidation wave is an alkynyl ligand-centered oxidation, while the first reduction couple is ascribed to a ligand-centered reduction of the cyclometalated ligand with the exception of 3 in which the first reduction couple is assigned as an alkynyl ligand-centered reduction. Their electronic absorption and luminescence behaviors have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the π-π* intraligand (IL) transition of the cyclometalated RC^N(R')^CR ligand with some mixing of a [π(C≡CR'') -> π*(RC^N(R')^CR)] ligand-to-ligand charge transfer (LLCT) character. The low-energy emission bands of all the complexes, with the exception of 5, are ascribed to origins mainly derived from the π-π* IL transition of the cyclometalated RC^N(R')^CR ligand. In the case of 5 that contains an electron-rich amino substituent on the alkynyl ligand, the low-energy emission band was found to show an obvious shift to the red. A change in the origin of emission is evident, and the emission of 5 is tentatively ascribed to a [π(C≡CC6H4NH2) -> π*(C^N^C)] LLCT excited-state origin. DFT and TDDFT computational studies have been performed to verify and elucidate the results of the electrochemical and photophysical studies.-
dc.languageengen_HK
dc.publisherAmerican Chemical Society.en_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.subjectLigand centered reduction-
dc.subjectOxidation wave-
dc.subjectPhotophysical-
dc.subjectX ray crystal structures-
dc.subjectComplexation-
dc.titleA class of luminescent cyclometalated alkynylgold(III) complexes: synthesis, characterization, and electrochemical, photophysical, and computational studies of [Au(C^N^C)(C≡C-R)] (C^N^C = κ(3)C,N,C bis-cyclometalated 2,6-diphenylpyridyl)en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0002-7863&volume=129&spage=4350&epage=4365&date=2007&atitle=A+Class+of+Luminescent+Cyclometalated+Alkynylgold(III) Complexes:+Synthesis,+Characterization,+and+Electrochemical,+Photophysical,+and+Computational+Studies+of+[Au(CNC)CbaC-R]+(CNC++=+k3C,N,C+Bis-cyclometalated+2,6-Diphenylpyridyl)en_HK
dc.identifier.emailWong, KMC: wongmc@hku.hken_HK
dc.identifier.emailLam, WH: chsue@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailYam, VWW: wwyam@hku.hken_HK
dc.identifier.authorityWong, MC=rp00809en_HK
dc.identifier.authorityLam, SWH=rp00719en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityYam, VWW=rp00822en_HK
dc.identifier.doi10.1021/ja068264u-
dc.identifier.pmid17362007-
dc.identifier.scopuseid_2-s2.0-34247121080-
dc.identifier.hkuros131616en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-34247121080&selection=ref&src=s&origin=recordpage-
dc.identifier.volume129-
dc.identifier.issue14-
dc.identifier.spage4350-
dc.identifier.epage4365-
dc.identifier.isiWOS:000245723800050-
dc.publisher.placeUnited States-
dc.relation.erratumdoi:10.1021/ja0768993-
dc.identifier.scopusauthoridWong, KMC=8061067200-
dc.identifier.scopusauthoridHung, LL=8528992200-
dc.identifier.scopusauthoridWai, HL=22433970100-
dc.identifier.scopusauthoridZhu, N=7201449530-
dc.identifier.scopusauthoridYam, VWW=18539304700-
dc.customcontrol.immutablecsl 130730-

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