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Article: Structural variations and spectroscopic properties of luminescent mono- and multinuclear silver(I) and copper(I) complexes bearing phosphine and cyanide ligands

TitleStructural variations and spectroscopic properties of luminescent mono- and multinuclear silver(I) and copper(I) complexes bearing phosphine and cyanide ligands
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2005, v. 44 n. 5, p. 1511-1524 How to Cite?
AbstractReaction of equimolar amounts of AgCN and PCy 3 gave the polymer [(Cy 3P)Ag(NCAgCN)]∞ (1), whereas employment of excess PCy 3 yielded the discrete compound [(Cy 3P) 2Ag(NCAgCN)] (2). Reacting bis(dicyclohexylphosphino)-methane (dcpm) with AgCN in 1:1 and 1:2 molar ratios gave two crystalline forms, namely [Ag 2(μ-dcpm) 2][Ag-(CN) 2] 2· (CH 3OH) 2 (3a·(CH 3OH) 2) and [Ag 2(μ-dcpm) 2][Ag(CN) 2] 2 (3b), respectively. The similar reaction of CuCN with PCy 3 afforded the polymeric compound [{(Cy 3P)Cu(CN)} 3]∞ (4), whereas treatment of CuCN with dcpm gave [Cu 2(μ-dcpm) 2(CN) 2] (5). Employment of diphosphine ligands with longer -(CH 2) n- spacers, such as 1,2-bis-(dicyclohexylphosphino) ethane (dcpe, n = 2) and 1,3-bis(diphenylphosphino)propane (dppp, n = 3), in reactions with [Cu(CH 3CN) 4]PF 6 and KCN afforded the macrocylic compounds [{Cu(dcpe)} 2(CN)(μ-dcpe)]PF 6 (6(PF 6)) and [{Cu(dppp)} 3(CN) 2(μ-dppp)] PF 6 (7(PF 6)), respectively. The hexanuclear complex [Cu(CN)(PCy 3)] 6 (8) was obtained by reacting CuCN with PCy 3 in the presence of sodium pyridine-2-thiolate. The UV-vis absorption spectrum of 1 in acetonitrile displays a weak shoulder at 245 nm (ε = 350 dm 3 mol -1 cm -1). For 3a, 3b, and 5, the intense absorption bands at λ max = 257-276 nm with ε values of (1.73-1.80) × 10 4 dm 3 mol -1 cm -1 are assigned to [ndσ* → (n + 1)pσ] transitions. Complexes 3a and 3b emit at λ max = 365 nm in CH 3CN (quantum yield ∼6 × 10 -3, lifetime ∼0.2 μs). The solid-state emission of 5 (λ max = 470 and 488 nm at 298 and 77 K) is red-shifted in energy from that of 4 (λ max = 401 and 405 nm at 298 and 77 K, respectively). In 77 K MeOH/EtOH (1:4) glassy solution, complexes 4-8 display intense emission with λ max at 382-416 nm, which is assigned to the [3d → (4s, 4p)] triplet excited state. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/70098
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLin, YYen_HK
dc.contributor.authorLai, SWen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorFu, WFen_HK
dc.contributor.authorZhou, ZYen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2010-09-06T06:19:42Z-
dc.date.available2010-09-06T06:19:42Z-
dc.date.issued2005en_HK
dc.identifier.citationInorganic Chemistry, 2005, v. 44 n. 5, p. 1511-1524en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70098-
dc.description.abstractReaction of equimolar amounts of AgCN and PCy 3 gave the polymer [(Cy 3P)Ag(NCAgCN)]∞ (1), whereas employment of excess PCy 3 yielded the discrete compound [(Cy 3P) 2Ag(NCAgCN)] (2). Reacting bis(dicyclohexylphosphino)-methane (dcpm) with AgCN in 1:1 and 1:2 molar ratios gave two crystalline forms, namely [Ag 2(μ-dcpm) 2][Ag-(CN) 2] 2· (CH 3OH) 2 (3a·(CH 3OH) 2) and [Ag 2(μ-dcpm) 2][Ag(CN) 2] 2 (3b), respectively. The similar reaction of CuCN with PCy 3 afforded the polymeric compound [{(Cy 3P)Cu(CN)} 3]∞ (4), whereas treatment of CuCN with dcpm gave [Cu 2(μ-dcpm) 2(CN) 2] (5). Employment of diphosphine ligands with longer -(CH 2) n- spacers, such as 1,2-bis-(dicyclohexylphosphino) ethane (dcpe, n = 2) and 1,3-bis(diphenylphosphino)propane (dppp, n = 3), in reactions with [Cu(CH 3CN) 4]PF 6 and KCN afforded the macrocylic compounds [{Cu(dcpe)} 2(CN)(μ-dcpe)]PF 6 (6(PF 6)) and [{Cu(dppp)} 3(CN) 2(μ-dppp)] PF 6 (7(PF 6)), respectively. The hexanuclear complex [Cu(CN)(PCy 3)] 6 (8) was obtained by reacting CuCN with PCy 3 in the presence of sodium pyridine-2-thiolate. The UV-vis absorption spectrum of 1 in acetonitrile displays a weak shoulder at 245 nm (ε = 350 dm 3 mol -1 cm -1). For 3a, 3b, and 5, the intense absorption bands at λ max = 257-276 nm with ε values of (1.73-1.80) × 10 4 dm 3 mol -1 cm -1 are assigned to [ndσ* → (n + 1)pσ] transitions. Complexes 3a and 3b emit at λ max = 365 nm in CH 3CN (quantum yield ∼6 × 10 -3, lifetime ∼0.2 μs). The solid-state emission of 5 (λ max = 470 and 488 nm at 298 and 77 K) is red-shifted in energy from that of 4 (λ max = 401 and 405 nm at 298 and 77 K, respectively). In 77 K MeOH/EtOH (1:4) glassy solution, complexes 4-8 display intense emission with λ max at 382-416 nm, which is assigned to the [3d → (4s, 4p)] triplet excited state. © 2005 American Chemical Society.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleStructural variations and spectroscopic properties of luminescent mono- and multinuclear silver(I) and copper(I) complexes bearing phosphine and cyanide ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=44&spage=1511&epage=1524&date=2005&atitle=Structural+variations+and+spectroscopic+properties+of+luminescent+mono-and+multinuclear+silver(I)+and+copper(I)+complexes+bearing+phosphine+and+cyanide+ligandsen_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_fulltext-
dc.identifier.doi10.1021/ic048876ken_HK
dc.identifier.pmid15732994-
dc.identifier.scopuseid_2-s2.0-14744298198en_HK
dc.identifier.hkuros98420en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-14744298198&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume44en_HK
dc.identifier.issue5en_HK
dc.identifier.spage1511en_HK
dc.identifier.epage1524en_HK
dc.identifier.isiWOS:000227346300053-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLin, YY=7406585692en_HK
dc.identifier.scopusauthoridLai, SW=55104882100en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridFu, WF=7202947315en_HK
dc.identifier.scopusauthoridZhou, ZY=7406096262en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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