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Article: Luminescent alkynylplatinum(II) complexes of 2,6-bis(N-alkylbenzimidazol- 2′-yl)pyridine-type ligands with ready tunability of the nature of the emissive states by solvent and electronic property modulation

TitleLuminescent alkynylplatinum(II) complexes of 2,6-bis(N-alkylbenzimidazol- 2′-yl)pyridine-type ligands with ready tunability of the nature of the emissive states by solvent and electronic property modulation
Authors
KeywordsAlkynyl ligands
Computer chemistry
Density functional calculations
N ligands
Photoluminescence
Platinum
Issue Date2008
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, 2008, v. 14 n. 15, p. 4562-4576 How to Cite?
AbstractA new class of luminescent alkynylplatinum(II) complexes of tri-dentate bis(N-alkylbenzimidazol-2′-yl)-pyridines (bzimpy), [Pt(R,R′-bzimpy)- (C≡C-R″)]X (X = PF6, OTf), and one of their chloro precursor complexes, [Pt(R,R′-bzimpy)Cl]PF6, have been synthesized and characterized; one of the alkynyl complexes has also been structurally characterized by X-ray crystallography. Electrochemical studies showed that the oxidation wave is alkynyl ligand-based in nature with some mixing of the metal center-based contribution, whereas the two quasi-reversible reduction couples are mainly bzimpy-based reductions. The electronic absorption and luminescence properties of the complexes have also been investigated. In solution, the high-energy and intense absorption bands are assigned as the π-π* intraligand (IL) transitions of the bzimpy and alkynyl ligands, whereas the low-energy and moderately intense absorptions are assigned to an admixture of metal-to-ligand charge-transfer (MLCT) (dπ(Pt) →π*(R,R′-bzimpy)) and ligand-to-ligand charge-transfer (LLCT) (π-(C≡C-R″) →* (R,R′-bzimpy)) transitions. Upon variation of the electronic effects of the arylalkynyl ligands, vibronic-structured or structureless emission bands, originating from triplet metal-perturbed intraligand (IL) or an admixture of triplet metal-to-ligand charge-transfer (MLCT) and ligand-to-ligand charge-transfer (LLCT) excited states respectively, were observed in solution. Interestingly, two of the complexes showed a dual luminescence that was sensitive to the polarity of the solvents. Upon cooling from 298 K to 155 K, drastic color, UV/Vis, and luminescence changes were observed in a butyronitrile solution of 1, and were ascribed to the formation of aggregate species through Pt ⋯ Pt and π-π stacking interactions. DFT and time-dependent DFT (TD-DFT) calculations have been performed to verify and elucidate the results of the electrochemical and photophysical properties. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/69835
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorTam, AYYen_HK
dc.contributor.authorLam, WHen_HK
dc.contributor.authorWong, KMCen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorYam, VWWen_HK
dc.date.accessioned2010-09-06T06:17:16Z-
dc.date.available2010-09-06T06:17:16Z-
dc.date.issued2008en_HK
dc.identifier.citationChemistry - A European Journal, 2008, v. 14 n. 15, p. 4562-4576en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69835-
dc.description.abstractA new class of luminescent alkynylplatinum(II) complexes of tri-dentate bis(N-alkylbenzimidazol-2′-yl)-pyridines (bzimpy), [Pt(R,R′-bzimpy)- (C≡C-R″)]X (X = PF6, OTf), and one of their chloro precursor complexes, [Pt(R,R′-bzimpy)Cl]PF6, have been synthesized and characterized; one of the alkynyl complexes has also been structurally characterized by X-ray crystallography. Electrochemical studies showed that the oxidation wave is alkynyl ligand-based in nature with some mixing of the metal center-based contribution, whereas the two quasi-reversible reduction couples are mainly bzimpy-based reductions. The electronic absorption and luminescence properties of the complexes have also been investigated. In solution, the high-energy and intense absorption bands are assigned as the π-π* intraligand (IL) transitions of the bzimpy and alkynyl ligands, whereas the low-energy and moderately intense absorptions are assigned to an admixture of metal-to-ligand charge-transfer (MLCT) (dπ(Pt) →π*(R,R′-bzimpy)) and ligand-to-ligand charge-transfer (LLCT) (π-(C≡C-R″) →* (R,R′-bzimpy)) transitions. Upon variation of the electronic effects of the arylalkynyl ligands, vibronic-structured or structureless emission bands, originating from triplet metal-perturbed intraligand (IL) or an admixture of triplet metal-to-ligand charge-transfer (MLCT) and ligand-to-ligand charge-transfer (LLCT) excited states respectively, were observed in solution. Interestingly, two of the complexes showed a dual luminescence that was sensitive to the polarity of the solvents. Upon cooling from 298 K to 155 K, drastic color, UV/Vis, and luminescence changes were observed in a butyronitrile solution of 1, and were ascribed to the formation of aggregate species through Pt ⋯ Pt and π-π stacking interactions. DFT and time-dependent DFT (TD-DFT) calculations have been performed to verify and elucidate the results of the electrochemical and photophysical properties. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.en_HK
dc.languageengen_HK
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.subjectAlkynyl ligandsen_HK
dc.subjectComputer chemistryen_HK
dc.subjectDensity functional calculationsen_HK
dc.subjectN ligandsen_HK
dc.subjectPhotoluminescenceen_HK
dc.subjectPlatinumen_HK
dc.subject.meshAlkynes - chemistry-
dc.subject.meshComputer Simulation-
dc.subject.meshLuminescence-
dc.subject.meshOrganoplatinum Compounds - chemical synthesis - chemistry-
dc.subject.meshPyridines - chemistry-
dc.titleLuminescent alkynylplatinum(II) complexes of 2,6-bis(N-alkylbenzimidazol- 2′-yl)pyridine-type ligands with ready tunability of the nature of the emissive states by solvent and electronic property modulationen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=14&issue=15&spage=4562&epage=4576&date=2008&atitle=Luminescent+alkynylplatinum(II)+complexes+of+2,6-bis(N-alkylbenzimidazol-+2′-yl)pyridine-type+ligands+with+ready+tunability+of+the+nature+of+the+emissive+states+by+solvent+and+electronic+property+modulationen_HK
dc.identifier.emailLam, WH: chsue@hku.hken_HK
dc.identifier.emailWong, KMC: wongmc@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailYam, VWW: wwyam@hku.hken_HK
dc.identifier.authorityLam, WH=rp00719en_HK
dc.identifier.authorityWong, KMC=rp00809en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityYam, VWW=rp00822en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200701914en_HK
dc.identifier.pmid18393346en_HK
dc.identifier.scopuseid_2-s2.0-53849131349en_HK
dc.identifier.hkuros147559en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-53849131349&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume14en_HK
dc.identifier.issue15en_HK
dc.identifier.spage4562en_HK
dc.identifier.epage4576en_HK
dc.identifier.isiWOS:000256241700014-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridTam, AYY=16643873800en_HK
dc.identifier.scopusauthoridLam, WH=26642862800en_HK
dc.identifier.scopusauthoridWong, KMC=8061067200en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridYam, VWW=18539304700en_HK

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