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Article: Syntheses, electronic absorption, emission, and ion-binding studies of platinum(II) C^N^C and terpyridyl complexes containing crown ether pendants

TitleSyntheses, electronic absorption, emission, and ion-binding studies of platinum(II) C^N^C and terpyridyl complexes containing crown ether pendants
Authors
KeywordsCrown compounds
Ion-binding
N ligands
Platinum terpyridine
Issue Date2002
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2002, v. 8 n. 17, p. 4066-4076 How to Cite?
AbstractA series of platinum (II) C^N^C complexes, [Pt(C^N^C) (L)] (HC^N^CH = 2,6-diphenylpyridine (dppy); L=Ph2PB15C5 (1, B15C5= benzo[15]crown-5), Ph2PDMP (2, DMP =3,4-dimethoxyphenyl), pyCOA15C5 (3, A15C5=aza[15]crown-5), pyCON-(CH2CH2OCH3)2 (4), pyC≡CB15C5 (5), pyC≡CDMP (6)) and terpyridyl complexes, [Pt(trpy)(L)](X)2 (trpy= 2,2′:6′,2″-terpyridine; L=Ph2PB15C5, X=OTf (7a), PF6 (7b); X=PF6, L= Ph2PDMP (8), pyC≡CB15C5 (9), and pyC≡CDMP (10)) have been successfully synthesized and characterized. The structures of 1, 3, and 7a have been determined by X-ray crystallography. Excitation of complexes 1-6 in EtOH/ MeOH (4:1 v/v) glass gave high-energy structured emission bands, assigned as derived from states of metal-perturbed intraligand (IL) origin. At higher concentrations, complexes 3-6 each displayed an additional, structureless emission band at 600-615 nm, with complexes 5 and 6 showing an obvious increase in the intensity of this emission band when the concentration was increased further. In dichloromethane at room temperature, complexes 3-6 showed, in addition to the high-energy emission at 490-505 nm, an extra, broad emission band at 620-625 nm when the concentration was increased. The emission origins of the low-energy band in glass and in fluid solutions are suggested to be derived from the ground-state oligomerization or aggregation process of the complexes. In the solid state at room temperature, complexes 1-6 each showed a broad, unstructured emission band at 560-600 nm, which was shifted to lower energy upon cooling to 77 K. On the other hand, the terpyridyl analogues 7-10 displayed intense vibronic-structured intraligand (IL) emissions at 460-472 nm in butyronitrile glass at 77 K. Solid-state samples of 9 and 10 displayed strong phosphorescence upon photoexcitation at 298 K and 77 K, tentatively assigned as derived from states of Pt(dπ)→π*(trpy) 3MLCT origin (MLCT = metal-to-ligand charge transfer). The ion-binding properties of complexes 5 and 9 for Na+, Ba2+, and K+ ions have been studied by UVNis spectrophotometric methods, and confirmed by ESI mass spectrometric studies. The ion-binding properties for Na+ ions have also been probed by 1H NMR experiments. For the same crown ether-containing ligand and the same metal ions, the neutral cyclometalated complexes gave larger binding constants than the positively charged terpyridyl analogues.
Persistent Identifierhttp://hdl.handle.net/10722/167744
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorYam, VWWen_HK
dc.contributor.authorTang, RPLen_HK
dc.contributor.authorWong, KMCen_HK
dc.contributor.authorLu, XXen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-10-08T03:10:52Z-
dc.date.available2012-10-08T03:10:52Z-
dc.date.issued2002en_HK
dc.identifier.citationChemistry - A European Journal, 2002, v. 8 n. 17, p. 4066-4076en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167744-
dc.description.abstractA series of platinum (II) C^N^C complexes, [Pt(C^N^C) (L)] (HC^N^CH = 2,6-diphenylpyridine (dppy); L=Ph2PB15C5 (1, B15C5= benzo[15]crown-5), Ph2PDMP (2, DMP =3,4-dimethoxyphenyl), pyCOA15C5 (3, A15C5=aza[15]crown-5), pyCON-(CH2CH2OCH3)2 (4), pyC≡CB15C5 (5), pyC≡CDMP (6)) and terpyridyl complexes, [Pt(trpy)(L)](X)2 (trpy= 2,2′:6′,2″-terpyridine; L=Ph2PB15C5, X=OTf (7a), PF6 (7b); X=PF6, L= Ph2PDMP (8), pyC≡CB15C5 (9), and pyC≡CDMP (10)) have been successfully synthesized and characterized. The structures of 1, 3, and 7a have been determined by X-ray crystallography. Excitation of complexes 1-6 in EtOH/ MeOH (4:1 v/v) glass gave high-energy structured emission bands, assigned as derived from states of metal-perturbed intraligand (IL) origin. At higher concentrations, complexes 3-6 each displayed an additional, structureless emission band at 600-615 nm, with complexes 5 and 6 showing an obvious increase in the intensity of this emission band when the concentration was increased further. In dichloromethane at room temperature, complexes 3-6 showed, in addition to the high-energy emission at 490-505 nm, an extra, broad emission band at 620-625 nm when the concentration was increased. The emission origins of the low-energy band in glass and in fluid solutions are suggested to be derived from the ground-state oligomerization or aggregation process of the complexes. In the solid state at room temperature, complexes 1-6 each showed a broad, unstructured emission band at 560-600 nm, which was shifted to lower energy upon cooling to 77 K. On the other hand, the terpyridyl analogues 7-10 displayed intense vibronic-structured intraligand (IL) emissions at 460-472 nm in butyronitrile glass at 77 K. Solid-state samples of 9 and 10 displayed strong phosphorescence upon photoexcitation at 298 K and 77 K, tentatively assigned as derived from states of Pt(dπ)→π*(trpy) 3MLCT origin (MLCT = metal-to-ligand charge transfer). The ion-binding properties of complexes 5 and 9 for Na+, Ba2+, and K+ ions have been studied by UVNis spectrophotometric methods, and confirmed by ESI mass spectrometric studies. The ion-binding properties for Na+ ions have also been probed by 1H NMR experiments. For the same crown ether-containing ligand and the same metal ions, the neutral cyclometalated complexes gave larger binding constants than the positively charged terpyridyl analogues.en_HK
dc.languageengen_US
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectCrown compoundsen_HK
dc.subjectIon-bindingen_HK
dc.subjectN ligandsen_HK
dc.subjectPlatinum terpyridineen_HK
dc.subject.meshCrystallography, X-Rayen_US
dc.subject.meshEthers, Cyclic - Chemistryen_US
dc.subject.meshModels, Chemicalen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshPlatinum Compounds - Chemical Synthesis - Chemistryen_US
dc.subject.meshPyridines - Chemistryen_US
dc.subject.meshSpectrum Analysisen_US
dc.titleSyntheses, electronic absorption, emission, and ion-binding studies of platinum(II) C^N^C and terpyridyl complexes containing crown ether pendantsen_HK
dc.typeArticleen_HK
dc.identifier.emailYam, VWW: wwyam@hku.hken_HK
dc.identifier.emailWong, KMC: wongmc@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityYam, VWW=rp00822en_HK
dc.identifier.authorityWong, KMC=rp00809en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1002/1521-3765(20020902)8:17<4066::AID-CHEM4066>3.0.CO;2-Oen_HK
dc.identifier.pmid12374091-
dc.identifier.scopuseid_2-s2.0-0037009107en_HK
dc.identifier.hkuros76034-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037009107&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume8en_HK
dc.identifier.issue17en_HK
dc.identifier.spage4066en_HK
dc.identifier.epage4076en_HK
dc.identifier.isiWOS:000177888300026-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridYam, VWW=18539304700en_HK
dc.identifier.scopusauthoridTang, RPL=7202300162en_HK
dc.identifier.scopusauthoridWong, KMC=8061067200en_HK
dc.identifier.scopusauthoridLu, XX=7404839171en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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