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- Publisher Website: 10.1002/1521-3765(20020902)8:17<4066::AID-CHEM4066>3.0.CO;2-O
- Scopus: eid_2-s2.0-0037009107
- PMID: 12374091
- WOS: WOS:000177888300026
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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
Title | Syntheses, electronic absorption, emission, and ion-binding studies of platinum(II) C^N^C and terpyridyl complexes containing crown ether pendants |
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Authors | |
Keywords | Crown compounds Ion-binding N ligands Platinum terpyridine |
Issue Date | 2002 |
Publisher | Wiley - 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? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/167744 |
ISSN | 2023 Impact Factor: 3.9 2023 SCImago Journal Rankings: 1.058 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Yam, VWW | en_HK |
dc.contributor.author | Tang, RPL | en_HK |
dc.contributor.author | Wong, KMC | en_HK |
dc.contributor.author | Lu, XX | en_HK |
dc.contributor.author | Cheung, KK | en_HK |
dc.contributor.author | Zhu, N | en_HK |
dc.date.accessioned | 2012-10-08T03:10:52Z | - |
dc.date.available | 2012-10-08T03:10:52Z | - |
dc.date.issued | 2002 | en_HK |
dc.identifier.citation | Chemistry - A European Journal, 2002, v. 8 n. 17, p. 4066-4076 | en_HK |
dc.identifier.issn | 0947-6539 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/167744 | - |
dc.description.abstract | A 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.language | eng | en_US |
dc.publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry | en_HK |
dc.relation.ispartof | Chemistry - A European Journal | en_HK |
dc.subject | Crown compounds | en_HK |
dc.subject | Ion-binding | en_HK |
dc.subject | N ligands | en_HK |
dc.subject | Platinum terpyridine | en_HK |
dc.subject.mesh | Crystallography, X-Ray | en_US |
dc.subject.mesh | Ethers, Cyclic - Chemistry | en_US |
dc.subject.mesh | Models, Chemical | en_US |
dc.subject.mesh | Molecular Structure | en_US |
dc.subject.mesh | Platinum Compounds - Chemical Synthesis - Chemistry | en_US |
dc.subject.mesh | Pyridines - Chemistry | en_US |
dc.subject.mesh | Spectrum Analysis | en_US |
dc.title | Syntheses, electronic absorption, emission, and ion-binding studies of platinum(II) C^N^C and terpyridyl complexes containing crown ether pendants | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Yam, VWW: wwyam@hku.hk | en_HK |
dc.identifier.email | Wong, KMC: wongmc@hku.hk | en_HK |
dc.identifier.email | Zhu, N: nzhu@hkucc.hku.hk | en_HK |
dc.identifier.authority | Yam, VWW=rp00822 | en_HK |
dc.identifier.authority | Wong, KMC=rp00809 | en_HK |
dc.identifier.authority | Zhu, N=rp00845 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1002/1521-3765(20020902)8:17<4066::AID-CHEM4066>3.0.CO;2-O | en_HK |
dc.identifier.pmid | 12374091 | - |
dc.identifier.scopus | eid_2-s2.0-0037009107 | en_HK |
dc.identifier.hkuros | 76034 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0037009107&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 8 | en_HK |
dc.identifier.issue | 17 | en_HK |
dc.identifier.spage | 4066 | en_HK |
dc.identifier.epage | 4076 | en_HK |
dc.identifier.isi | WOS:000177888300026 | - |
dc.publisher.place | Germany | en_HK |
dc.identifier.scopusauthorid | Yam, VWW=18539304700 | en_HK |
dc.identifier.scopusauthorid | Tang, RPL=7202300162 | en_HK |
dc.identifier.scopusauthorid | Wong, KMC=8061067200 | en_HK |
dc.identifier.scopusauthorid | Lu, XX=7404839171 | en_HK |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_HK |
dc.identifier.scopusauthorid | Zhu, N=7201449530 | en_HK |
dc.identifier.issnl | 0947-6539 | - |