English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/64722
Share/Impact:
Statistics
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:
DC FieldValueLanguage
dc.contributor.authorSicilia, Violeta-
dc.contributor.authorForniés, Juan-
dc.contributor.authorCasas, José M.-
dc.contributor.authorMartín, Antonio-
dc.contributor.authorLópez, José A.-
dc.contributor.authorLarraz, Carmen-
dc.contributor.authorBorja, Pilar-
dc.contributor.authorOvejero, Carmen-
dc.date.accessioned2013-01-22T13:57:07Z-
dc.date.available2013-01-22T13:57:07Z-
dc.date.issued2012-
dc.identifierdoi: 10.1021/ic201910t-
dc.identifierissn: 0020-1669-
dc.identifiere-issn: 1520-510X-
dc.identifier.citationInorganic Chemistry 51(6): 3427-3435 (2012)-
dc.identifier.urihttp://hdl.handle.net/10261/64722-
dc.description.abstractThe half-lantern compound [{Pt(bzq)(μ-C 7H 4NS 2-κN,S)} 2]•Me 2CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC 7H 4NS 2) and [Pt(bzq)(NCMe) 2]ClO 4. The Pt(II)•••Pt(II) separation in the neutral complex [{Pt(bzq)(μ-C 7H 4NS 2-κN,S)} 2] is 2.910 (2) Å, this being among the shortest observed in half-lantern divalent platinum complexes. Within the complex, the benzo[h]quinoline (bzq) groups lie in close proximity with most C•••C distances being between 3.3 and 3.7 Å, which is indicative of significant π-π interactions. The reaction of 1 with halogens X 2 (X 2 = Cl 2, Br 2, or I 2) proceeds with a two-electron oxidation to give the corresponding dihalodiplatinum(III) complexes [{Pt(bzq)(μ-C 7H 4NS 2-κN,S)X} 2] (X = Cl 2, Br 3, I 4). Their X-ray structures confirm the retention of the half-lantern structure and the coordination mode of the bzq and the bridging ligand μ-C 7H 4NS 2-κN,S. The Pt-Pt distances (Pt-Pt = 2.6420(3) Å 2, 2.6435(4) Å 3, 2.6690(3) Å 4) are shorter than that in 1 because of the Pt-Pt bond formation. Time dependent-density functional theory (TD-DFT) studies performed on 1 show a formal bond order of 0 between the metal atoms, with the 6p z contribution diminishing the antibonding character of the highest occupied molecular orbital (HOMO) and being responsible for an attractive intermetallic interaction. A shortening of the Pt-Pt distance from 2.959 Å in the ground state S 0 to 2.760 Å in the optimized first excited state (T 1) is consistent with an increase in the Pt-Pt bond order to 0.5. In agreement with TD-DFT calculations, the intense, structureless, red emission of 1 in the solid state and in solution can be mainly attributed to triplet metal-metal-to-ligand charge transfer ( 3MMLCT) [dσ(Pt-Pt) → π(bzq)] excited states. The high quantum yields of this emission measured in toluene (44%) and solid state (62%) at room temperature indicate that 1 is a very efficient and stable 3MMLCT emitter, even in solution. The high luminescence quantum yield of its red emission, added to its neutral character and the thermal stability of 1, make it a potential compound to be incorporated as phosphorescent dopant in multilayer organic light-emitting devices (OLEDs). © 2012 American Chemical Society.-
dc.description.sponsorshipThis work was supported by the Spanish MICINN/FEDER (Project CTQ2008-06669-C02), MICINN/FEDER (Project CTQ2008-03860), and the Gobierno de Aragón (Grupo Consolidado: Química Inorgánica y de los Compuestos Organometálicos). D.T. and P. B. acknowledge the support of a FPU and FPI grants, respectively, from the MICINN. -
dc.language.isoeng-
dc.publisherAmerican Chemical Society-
dc.rightsclosedAccess-
dc.titleHighly luminescent half-lantern cyclometalated platinum(II) complex: Synthesis, structure, luminescence studies, and reactivity-
dc.typeartículo-
dc.identifier.doi10.1021/ic201910t-
dc.date.updated2013-01-22T13:57:07Z-
dc.description.versionPeer Reviewed-
Appears in Collections:(ISQCH) Artículos
Files in This Item:
File Description SizeFormat 
accesoRestringido.pdf15,38 kBAdobe PDFThumbnail
View/Open
Show simple item record
 

Related articles:


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.