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Article: Luminescent tetranuclear silver(I) arylacetylide complexes bearing tricyclohexylphosphine ligands: Synthesis, molecular structures, and spectroscopic comparison with gold(I) and copper(I) arylacetylides

TitleLuminescent tetranuclear silver(I) arylacetylide complexes bearing tricyclohexylphosphine ligands: Synthesis, molecular structures, and spectroscopic comparison with gold(I) and copper(I) arylacetylides
Authors
Issue Date2002
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2002, v. 21 n. 11, p. 2275-2282 How to Cite?
AbstractA series of luminescent tetranuclear silver(I) arylacetylides [Ag4[μ(C≡C)xC6H4R-p)4 }-(PCy3)y (x = 1, y = 2, R = H (1), CH3 (2), OCH3 (3), Cx≡CPh (5); x = 2, y = 4, R = H (4)) were synthesized by treatment of tricyclohexylphosphine (PCy3) with [Ag{(C≡C)xC6H4R-p}]∞ in dichloromethane in the absence of light, and their spectroscopic and photophysical properties have been investigated. The X-ray structure of 1 exhibits a planar parallelogram-like Ag4core and consists of [Ag(C≡CPh)2] and [Ag(PCy3)] fragments with phenylacetylide σ-coordinated to silver atoms in a μ2-bonding mode (mean asymmetric Ag-C(α) distances are 2.05 and 2.33 Å). For 2, 3, and 5, with different para substituents in the arylacetylide units, similar tetranuclear structures are observed. In contrast, the structure of 4 can be described as two interpenetrating tetrahedra of four silver atoms and four phenylbutadiynyl moieties forming a twisted cubane structure, with each silver atom further coordinated to a PCy3 ligand. The electronic absorption spectra of 1-5 in CH2Cl2 are dominated by strong, vibronically structured absorptions at 250-332 nm (ε 104-105 dm3 mol-1 cm-1) with vibrational spacings of 1420-2160 cm-1 which are attributed to v(C≡C) or admixtures of acetylenic and aryl stretching frequencies. The solid-state emission spectra of 1-3 at 298 and 77 K show intense vibronically structured bands at 422-607 nm which are attributed to 3(ππ*) excited states of the arylacetylide ligands. For 4, the solid-state emission is slightly red-shifted in energy from the 3(ππ*) emission of the corresponding mononuclear [Au(PCy3)-(C≡C-C≡CPh)] congener, whereas for 5, a red-shift in its emission is observed from that of 1-4. A comparison between the emission of Cu(I), Ag(I), and Au(I) arylacetylides is made.
Persistent Identifierhttp://hdl.handle.net/10722/69964
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLin, YYen_HK
dc.contributor.authorLai, SWen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorZhou, ZYen_HK
dc.date.accessioned2010-09-06T06:18:27Z-
dc.date.available2010-09-06T06:18:27Z-
dc.date.issued2002en_HK
dc.identifier.citationOrganometallics, 2002, v. 21 n. 11, p. 2275-2282en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69964-
dc.description.abstractA series of luminescent tetranuclear silver(I) arylacetylides [Ag4[μ(C≡C)xC6H4R-p)4 }-(PCy3)y (x = 1, y = 2, R = H (1), CH3 (2), OCH3 (3), Cx≡CPh (5); x = 2, y = 4, R = H (4)) were synthesized by treatment of tricyclohexylphosphine (PCy3) with [Ag{(C≡C)xC6H4R-p}]∞ in dichloromethane in the absence of light, and their spectroscopic and photophysical properties have been investigated. The X-ray structure of 1 exhibits a planar parallelogram-like Ag4core and consists of [Ag(C≡CPh)2] and [Ag(PCy3)] fragments with phenylacetylide σ-coordinated to silver atoms in a μ2-bonding mode (mean asymmetric Ag-C(α) distances are 2.05 and 2.33 Å). For 2, 3, and 5, with different para substituents in the arylacetylide units, similar tetranuclear structures are observed. In contrast, the structure of 4 can be described as two interpenetrating tetrahedra of four silver atoms and four phenylbutadiynyl moieties forming a twisted cubane structure, with each silver atom further coordinated to a PCy3 ligand. The electronic absorption spectra of 1-5 in CH2Cl2 are dominated by strong, vibronically structured absorptions at 250-332 nm (ε 104-105 dm3 mol-1 cm-1) with vibrational spacings of 1420-2160 cm-1 which are attributed to v(C≡C) or admixtures of acetylenic and aryl stretching frequencies. The solid-state emission spectra of 1-3 at 298 and 77 K show intense vibronically structured bands at 422-607 nm which are attributed to 3(ππ*) excited states of the arylacetylide ligands. For 4, the solid-state emission is slightly red-shifted in energy from the 3(ππ*) emission of the corresponding mononuclear [Au(PCy3)-(C≡C-C≡CPh)] congener, whereas for 5, a red-shift in its emission is observed from that of 1-4. A comparison between the emission of Cu(I), Ag(I), and Au(I) arylacetylides is made.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_HK
dc.relation.ispartofOrganometallicsen_HK
dc.titleLuminescent tetranuclear silver(I) arylacetylide complexes bearing tricyclohexylphosphine ligands: Synthesis, molecular structures, and spectroscopic comparison with gold(I) and copper(I) arylacetylidesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=21&spage=2275&epage=2282&date=2002&atitle=Luminescent+tetranuclear+silver(I)+arylacetylide+complexes+bearing+tricyclohexylphosphine+ligands:++synthesis,+molecular+structures,+and+spectroscopic+comparison+with+gold(I)+and+copper(I)+arylacetylidesen_HK
dc.identifier.emailLai, SW: swlai@hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityLai, SW=rp00717en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/om010835yen_HK
dc.identifier.scopuseid_2-s2.0-0000065473en_HK
dc.identifier.hkuros72430en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000065473&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume21en_HK
dc.identifier.issue11en_HK
dc.identifier.spage2275en_HK
dc.identifier.epage2282en_HK
dc.identifier.isiWOS:000175734300019-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLin, YY=7406585692en_HK
dc.identifier.scopusauthoridLai, SW=7402937200en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridZhou, ZY=7406096262en_HK

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