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Article: Luminescent mononuclear and binuclear cyclometalated palladium(II) complexes of 6-Phenyl-2,2'-bipyridines: Spectroscopic and structural comparisons with platinum(II) analogues 1,2

TitleLuminescent mononuclear and binuclear cyclometalated palladium(II) complexes of 6-Phenyl-2,2'-bipyridines: Spectroscopic and structural comparisons with platinum(II) analogues 1,2
Authors
Issue Date2000
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2000, v. 39 n. 2, p. 255-262 How to Cite?
AbstractThe mononuclear cyclometalated Pd(II) complexes [Pd(L 1)X] (HL 1 = 6-phenyl-2,2'-bipyridine; X = Cl, 1a; Br, 1b; I, 1c), [Pd(L 1)PPh 3] + (1d), [Pd(L 2-5)Cl] [2a-5a, HL 2-5 = 4-(aryl)-6-phenyl-2,2'-bipyridine; aryl = phenyl (2), 4-chlorophenyl (3), 4-tolyl (4), 4-methoxyphenyl (5)] and the binuclear derivatives [Pd 2(L 1-5) 2(μ-dppm)] 2+ (1e-5e, dppm = bis(diphenylphosphino)methane) and [Pd 2(L 1) 2(μ-dppC 5)] 2+, (1f, dppC 5 = 1,5-bis(diphenylphosphino)pentane) were prepared. The crystal structures of 1d(ClO 4), 1e(ClO 4) 2·DMF, and 2e(ClO 4) 2 have been determined by X-ray crystallography. The magnitude of the Pd-Pd distances in 1e and 2e (3.230(1) and 3.320(2) Å, respectively) suggest minimal metal-metal interaction, although π-stacking of the aromatic ligands (interplanar separations 3.34 and 3.35 Å, respectively) is evident. All complexes display low-energy UV absorptions at λ ~ 390 nm, which are tentatively assigned to 1MLCT transitions; red shifts resulting from Pd-Pd interactions in the binuclear species are not apparent. The complexes in this work are non-emissive at 298 K, but the cationic derivatives exhibit intense luminescence at 77 K. The structured emissions of 1d and 1f in MeOH/EtOH glass (λ(max) 467-586 nm) and all cationic species in the solid state (λ(max) 493-578 nm) are assigned to intraligand excited states. Complexes 1e-5e display dual emissions in MeOH/EtOH glass at 77 K, and the broad structureless bands at λ(max) 626-658 nm are attributed to π-π excimeric IL transitions. A comparison between the photophysical properties of Pd(II) and Pt(II) congeners is presented.
Persistent Identifierhttp://hdl.handle.net/10722/167668
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLai, SWen_HK
dc.contributor.authorCheung, TCen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorPeng, SMen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:09:42Z-
dc.date.available2012-10-08T03:09:42Z-
dc.date.issued2000en_HK
dc.identifier.citationInorganic Chemistry, 2000, v. 39 n. 2, p. 255-262en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167668-
dc.description.abstractThe mononuclear cyclometalated Pd(II) complexes [Pd(L 1)X] (HL 1 = 6-phenyl-2,2'-bipyridine; X = Cl, 1a; Br, 1b; I, 1c), [Pd(L 1)PPh 3] + (1d), [Pd(L 2-5)Cl] [2a-5a, HL 2-5 = 4-(aryl)-6-phenyl-2,2'-bipyridine; aryl = phenyl (2), 4-chlorophenyl (3), 4-tolyl (4), 4-methoxyphenyl (5)] and the binuclear derivatives [Pd 2(L 1-5) 2(μ-dppm)] 2+ (1e-5e, dppm = bis(diphenylphosphino)methane) and [Pd 2(L 1) 2(μ-dppC 5)] 2+, (1f, dppC 5 = 1,5-bis(diphenylphosphino)pentane) were prepared. The crystal structures of 1d(ClO 4), 1e(ClO 4) 2·DMF, and 2e(ClO 4) 2 have been determined by X-ray crystallography. The magnitude of the Pd-Pd distances in 1e and 2e (3.230(1) and 3.320(2) Å, respectively) suggest minimal metal-metal interaction, although π-stacking of the aromatic ligands (interplanar separations 3.34 and 3.35 Å, respectively) is evident. All complexes display low-energy UV absorptions at λ ~ 390 nm, which are tentatively assigned to 1MLCT transitions; red shifts resulting from Pd-Pd interactions in the binuclear species are not apparent. The complexes in this work are non-emissive at 298 K, but the cationic derivatives exhibit intense luminescence at 77 K. The structured emissions of 1d and 1f in MeOH/EtOH glass (λ(max) 467-586 nm) and all cationic species in the solid state (λ(max) 493-578 nm) are assigned to intraligand excited states. Complexes 1e-5e display dual emissions in MeOH/EtOH glass at 77 K, and the broad structureless bands at λ(max) 626-658 nm are attributed to π-π excimeric IL transitions. A comparison between the photophysical properties of Pd(II) and Pt(II) congeners is presented.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleLuminescent mononuclear and binuclear cyclometalated palladium(II) complexes of 6-Phenyl-2,2'-bipyridines: Spectroscopic and structural comparisons with platinum(II) analogues 1,2en_HK
dc.typeArticleen_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_fulltexten_US
dc.identifier.doi10.1021/ic991089gen_HK
dc.identifier.pmid11272533-
dc.identifier.scopuseid_2-s2.0-0034707530en_HK
dc.identifier.hkuros53193-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0034707530&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume39en_HK
dc.identifier.issue2en_HK
dc.identifier.spage255en_HK
dc.identifier.epage262en_HK
dc.identifier.isiWOS:000085010500016-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLai, SW=7402937200en_HK
dc.identifier.scopusauthoridCheung, TC=7103334175en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridPeng, SM=35464852200en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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