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Título: | Preparation of Pt-Tl clusters showing new geometries. X-ray, NMR and luminescence studies |
Autor: | Belío, Úrsula CSIC; Fuertes, Sara CSIC ORCID; Martín, Antonio CSIC ORCID | Fecha de publicación: | 2014 | Editor: | Royal Society of Chemistry (UK) | Citación: | Dalton Transactions 43(28): 10828-10843 (2014) | Resumen: | Square planar complexes [Pt(CNC)L] (CNC = C,N,C-2,6-NC5H 3(C6H4-2)2; L = tht (tetrahydrothiophene, SC4H8, 1), L = CNtBu (2)) react with TlPF6 in different Pt/Tl molar ratios (3/1 in the case of 1 and 1/1 in the case of 2) yielding the complexes [{Pt(CNC)(tht)} 3Tl](PF6) (3) and [Pt(CNC)(CNtBu)Tl](PF 6) (4), respectively. The structures of 3 and 4 (X-ray) show the presence of Pt→Tl dative bonds unsupported by any bridging ligands. In complex 3, the only Tl centre is simultaneously bonded to three Pt atoms forming a perfect equilateral triangle with Pt-Tl distances of 2.9088(5) Å, remarkably short. Complex 4 is formed by three >Pt(CNC)(CN tBu)Tl> units, disposed in a triangular fashion, linked together through η6-Tl-arene interactions, and showing Pt-Tl bonds with distances of ca. 3.04 Å. The study of these crystal structures would seem to indicate that the difference between the Pt/Tl ratios found in the complexes 3 and 4 is due to the steric requirements of the L ligand bonded to Pt. NMR studies both in solution and in the solid state show that the Pt-Tl bond persists in solutions of 3 and 4. The UV-vis spectra of 3 and 4 in solution display the same profiles as those of 1 and 2, which may suggest a partial dissociation of the Pt-Tl bond in solution. However, by DFT calculations it was proved that in this case the formation of the Pt-Tl dative bond does not produce the expected blue-shift in the UV-vis absorptions. The emissive behaviour of 1-4 in the solid state and in frozen solutions is also studied and included in this work. © 2014 the Partner Organisations. | Versión del editor: | http://dx.doi.org/10.1039/C4DT00536H | URI: | http://hdl.handle.net/10261/111813 | DOI: | 10.1039/C4DT00536H | Identificadores: | doi: 10.1039/C4DT00536H issn: 1477-9226 e-issn: 1477-9234 |
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