000130314 001__ 130314
000130314 005__ 20240124152850.0
000130314 0247_ $$2doi$$a10.1039/b819323a
000130314 0248_ $$2sideral$$a114339
000130314 037__ $$aART-2009-114339
000130314 041__ $$aeng
000130314 100__ $$0(orcid)0000-0003-1374-5880$$aForniés, Juan$$uUniversidad de Zaragoza
000130314 245__ $$aExtended structures containing Pt(ii)–Tl(i) bonds. Effect of these interactions on the luminescence of cyclometalated Pt(ii) compounds
000130314 260__ $$c2009
000130314 5203_ $$aNeutralization reactions of the appropriate precursors (NBu<inf>4</inf>)[Pt(bzq)(C‚â°.tbd;C‚ÄìR)<inf>2</inf>] and (NBu<inf>4</inf>)[Pt(C‚ÅÅN)(CN)<inf>2</inf>] (C‚ÅÅN = bzq, ppy) with Tl<sup>I</sup> salts afford [(PtTl(bzq)(C‚â°.tbd;C‚ÄìR)<inf>2</inf>)<inf>2</inf>] [R = Ph (1), C<inf>5</inf>H<inf>4</inf>N-2 (2)] and [PtTl(C‚ÅÅN)(CN)<inf>2</inf>] [C‚ÅÅN = bzq (3), ppy (4)], respectively. X-Ray diffraction studies of complexes 2‚Äì4 show the existence of Pt<sup>II</sup>-Tl<sup>I</sup> bonds. In 2¬¿CH<inf>2</inf>Cl<inf>2</inf> the platinum‚Äìthallium units are associated in tetranuclear Pt<inf>2</inf>Tl<inf>2</inf> entities which generate a 3-D network through short Tl‚ãØŒ†(2-py) and Œ†‚ãØŒ†(bzq) contacts and additional weak Cl<inf>2</inf>HC‚ÄìH‚ãØŒ†(C‚â°.tbd;C) nonclassical interactions. Compounds 3 and 4 show extended 2-D networks by connection of the organometallic ‚ÄúPtTl(C‚ÅÅN)(CN)<inf>2</inf>‚Äù units, through secondary Tl‚ãØN‚â°.tbd;C contacts and moderate Œ†‚ãØŒ†(bzq) interactions in the case of 3. Complexes 1‚Äì3 containing the bzq group exhibit in the solid state ‚Äúluminescence thermochromism‚Äù associated to dual emission. At room temperature they show an intense, visible orange (1: Œõ<inf>max</inf> 625 nm), orange-red (2: Œõ<inf>max</inf> 640 nm) or yellow (3: Œõ<inf>max</inf> 582 nm) luminescence that changes to yellowish-green (1: Œõ<inf>max</inf> 532 nm) or green [2: Œõ<inf>max</inf> 524 nm; 3:<inf>max</inf> 512 nm] upon cooling to 77 K. The unstructured low energy (LE) bands attributed to <sup>3</sup>Œ†‚Ä쌆*excimeric emissions due to extensive Œ†‚Ä쌆 interactions are dominant at room temperature. By contrast, the high energy (HE) bands are highly structured and predominant at 77 K. Due to the presence of Pt‚ÄìTl bonds these HE emissions are bathochromically shifted in relation to the precursors‚Ä= ones and have been tentatively assigned to a metal-metal‚Ä=-to-ligand (bzq) charge transfer MM‚Ä=LCT [d/s œÉ*(Pt, Tl) ‚Ü팆*(C‚ÅÅN)] mixed, as in the corresponding precursors, with some intraligand <sup>3</sup>IL[Œ†(C‚ÅÅN‚Ä=) ‚Ü팆*(C‚ÅÅN)] in 3 and 4 or ligand-to-ligand charge transfer (alkynyl to bzq) <sup>3</sup>LL‚Ä=CT in complexes 1 and 2. Complex [PtTl(ppy)(CN)<inf>2</inf>] 4, which does not show short contacts between the phenylpyridinate groups in solid state, only shows the HE green structured band both at 298 K and at 77 K. Only the cyanide derivatives are soluble and both spectroscopic (NMR and UV-Vis) and emission data (MeOH, 298 K and 77 K) indicate that the Pt<sup>II</sup>‚ÄìTl<sup>I</sup> bond breaks down in solution. ¬© 2009 The Royal Society of Chemistry.
000130314 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000130314 590__ $$a4.081$$b2009
000130314 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 44 = 0.159$$c2009$$dQ1$$eT1
000130314 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000130314 700__ $$0(orcid)0000-0003-1812-3175$$aFuertes, Sara
000130314 700__ $$0(orcid)0000-0002-4808-574X$$aMartín, Antonio
000130314 700__ $$0(orcid)0000-0002-0257-0483$$aSicilia, Violeta$$uUniversidad de Zaragoza
000130314 700__ $$aGil, Belén
000130314 700__ $$aLalinde, Elena
000130314 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000130314 773__ $$g62, 12 (2009), 2224$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000130314 8564_ $$s549368$$uhttps://zaguan.unizar.es/record/130314/files/texto_completo.pdf$$yVersión publicada
000130314 8564_ $$s3269402$$uhttps://zaguan.unizar.es/record/130314/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
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000130314 951__ $$a2024-01-24-15:02:22
000130314 980__ $$aARTICLE