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2014

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Platinum(II) compounds containing cyclometalated tridentate ligands: Synthesis, luminescence studies, and a selective fluoro for methoxy substitution

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https://doi.org/10.1021/om401111t

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Two series of potentially tridentate ligands of formula ArCH=N(CH2)2NMe2 and ArCH=N(CH2)3NMe2 (Ar = C6H5, 2-FC6H4, 4-FC6H4, 2,3,4-F3C6H2) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl{Me2N(CH2)xN=CHR}] (3a−h), via the corresponding compounds [PtCl2{Me2N(CH2)xN=CHAr}] (2), requires drastic conditions and proceeds more easily for ligands derived from N,N-dimethylpropylenediamine (x = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F3C6H2CH=N(CH2)xNMe2. The syntheses of compounds [PtMe{Me2N(CH2)xN=CHR}] (4a−h) using [Pt2Me4(μ-SMe2)2] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl{Me2N(CH2)3N=CH(4-FC6H3)}] (3b) and [PtCl{Me2N-(CH2)3N=CH(2-OMe,3,4-F2C6H)}] (3g). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds 3) or at 77 K (compounds 4). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission.

Matèries

Platí, Lligands, Estructura molecular

Matèries (anglès)

Platinum, Ligands, Molecular structure

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Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)

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GANDIOSO, Albert, VALLE-SISTAC, J., RODRÍGUEZ RAURELL, Laura, CRESPO VICENTE, Margarita ma., FONT BARDIA, Ma. mercedes. Platinum(II) compounds containing cyclometalated tridentate ligands: Synthesis, luminescence studies, and a selective fluoro for methoxy substitution. _Organometallics_. 2014. Vol. 33, núm. 2, pàgs. 561-570. [consulta: 27 de desembre de 2025]. ISSN: 0276-7333. [Disponible a: https://hdl.handle.net/2445/165280]

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