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Título

N-assisted CPh-H activation in 3,8-dinitro-6- phenylphenanthridine. New C,N-cyclometalated compounds of platinum(II): Synthesis, structure, and luminescence studies

AutorSicilia, Violeta ; Fuertes, Sara ; Martín, Antonio ; Palacios, Adrián
Fecha de publicación2013
EditorAmerican Chemical Society
CitaciónOrganometallics 32(15): 4092-4102 (2013)
ResumenThe activation of a CPh-H bond in the phenyl ring of 3,8-dinitro-6-phenylphenanthridine (HCN) can be achieved by refluxing the intermediate [PtCl(η3-2-Me-C3H4)(HCN- κN)] (1) (η3-2-Me-C3H4 = η3-2-methylallyl) in 2-methoxyethanol to render the new cyclometalated complex [{Pt(μ-Cl)(CN)}2] (2). The cleavage of the bridging system in 2 by the neutral ligands L rendered the mononuclear complexes [PtCl(CN)L] (L = tht 3, PPh3 4, CNtBu 5) with the geometry (trans C, Cl).The air- and temperature-stable cationic compound [Pt(CN)(CNXyl)2]ClO4 (6) could be prepared from 2 by addition of CNXyl (1:4 molar ratio) after the Cl abstraction with AgClO 4. Compound [Pt(CN-κC)(tht)3]ClO4 (7) was prepared similarly to 6 but using a significant excess of tht, which produces the N-dissociation of the CN ligand. The photophysical properties of compounds 3-6 have been studied with the help of time-dependent density functional theory (TD-DFT) calculations. In 2-Me-THF at low temperature (77 K) the green emission of the HCN ligand turns to red phosphorescence in compounds 3-6, which was assigned to a mixed metal-to-ligand charge transfer/intraligand/ligand-to-ligand charge transfer [3MLCT/3IL/3L′LCT] excited state. In the solid state at low temperature (77 K) the emissive behaviors are quite similar to that observed in glassy solutions with some contribution of excimeric π-π* emissions in the neutral chloro derivatives. Compounds 4-6 are also emissive in the solid state at room temperature with photoluminescence quantum yields (Φ) between 0.032 and 0.05. © 2013 American Chemical Society.
Versión del editorhttp://dx.doi.org/10.1021/om400159g
URIhttp://hdl.handle.net/10261/111257
DOI10.1021/om400159g
Identificadoresdoi: 10.1021/om400159g
issn: 0276-7333
e-issn: 1520-6041
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