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Selective synthesis of new half-lantern benzoquinolate platinum complexes. DFT and photophysical studies on the platinum (II,II) derivative

AuthorsSicilia, Violeta ; Borja, Pilar ; Casas, José M. ; Fuertes, Sara ; Martín, Antonio
KeywordsX-ray study
Half-lantern compound
TD-DFT calculation
Coordination chemistry
Issue Date2013
CitationJournal of Organometallic Chemistry 731: 10-17 (2013)
AbstractThe half-lantern compound [{Pt(bzq)(μ-C7H4NOS- κN,S)}2] (2) (bzq = benzo[h]quinoline, C7H 4NOS = 2-mercaptobenzoxazolate) was prepared selectively by reaction of equimolar amounts of potassium 2-mercaptobenzoxazolate (KC7H 4NOS, 1) and [Pt(bzq)(NCMe)2]ClO4. Complex 2 undergoes two-electron oxidation by reaction with halogens X2 (X 2: Cl2, Br2 or I2) to give the corresponding dihalodiplatinum (III) complexes [{Pt(bzq)(μ-C 7H4NOS-κN,S)X}2] (X = Cl 3, Br 4, I 5). The X-ray structures of 3-5 confirm the retention of the half-lantern structure and the shortening of the Pt-Pt distance (Pt-Pt = 2.6383 (3) Å 3, =2.6671 (9) Å 4, 2.6810 (5) Å 5) with respect to that in 2 (2. 9726 (8) Å) because of the Pt-Pt bond formation. The trend of increasing Pt-Pt distances is in accordance with the trans-influence of the axial ligand (Cl < Br < I). DFT calculations on complex 2 in CH2Cl2 indicate the lowest energy absorption band to be mainly due to singlet metal-metal-to-ligand charge transfer (1MMLCT) [dσ *(Pt-Pt) → π*(bzq)] really affected by the π⋯π contacts in the complex, with just a little ligand-to-ligand charge transfer/intraligand (L'LCT/IL) character. The triplet 3MMLCT excited state seems to be the responsible of the structureless red emission of 2 in the solid state and in solution at room temperature. The quantum yield (90%) of this red emission in toluene solution at room temperature is really high. This fact added to the neutral character and the thermal stability of 2 make it a potential compound to be incorporated as phosphorescent dopant in multi-layer OLEDs. © 2013 Elsevier B.V. All rights reserved.
Publisher version (URL)http://dx.doi.org/10.1016/j.jorganchem.2013.01.027
Identifiersdoi: 10.1016/j.jorganchem.2013.01.027
issn: 0022-328X
Appears in Collections:(ISQCH) Artículos
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FIG1B.jpg64,85 kBJPEGThumbnail
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fig3b.pdf212,35 kBAdobe PDFThumbnail
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