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Heteroleptic cycloplatinated N-heterocyclic carbene complexes: A new approach to highly efficient blue-light emitters

AutorFuertes, Sara ; Chueca, Andrés J.; Arnal, Lorenzo; Martín, Antonio ; Giovanella, Umberto; Botta, Chiara; Sicilia, Violeta
Fecha de publicación2017
EditorAmerican Chemical Society
CitaciónInorganic Chemistry 56(9): 4829-4839 (2017)
ResumenNew heteroleptic compounds of platinum(II)-containing cyclometalated N-heterocyclic carbenes, [PtCl(R-C^C*)(PPh)] [R-CH^C*-κC* = 3-methyl-1-(naphthalen-2-yl)-1H-imidazol-2-ylidene (R-C = Naph; 1A), 1-[4-(ethoxycarbonyl)phenyl]-3-methyl-1H-imidazol-2-ylidene (R = COEt; 1B), and [Pt(R-C^C*)(py)(PPh)]PF (py = pyridine; R-C = Naph, 2A; R = COEt, 2B], have been prepared and fully characterized. All of them were obtained as the trans-(C*,PPh) isomer in high yields. The selectivity of their synthesis has been explained in terms of the degree of transphobia (T) of pairs of ligands in trans positions. X-ray diffraction studies on both 2A and 2B revealed that only in 2A, containing a C^C* with a more extended π system, do the molecules assemble themselves into head-to-tail pairs through intermolecular π···π contacts. The photophysical properties of 2A and 2B and those of the related compounds [Pt(NC-C^C*)(PPh)L]PF [NC-CH^C*-κC* = 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene; L = pyridine (py; 2C), 2,6-dimethylphenylisocyanide (CNXyl; 3C), and 2-mercapto-1-methylimidazole (MMI; 4C)] have been examined to analyze the influence of the R substituent on R-C^C* (R-C = Naph; R = COEt, CN) and that of the ancillary ligands (L) on them. Experimental data and time-dependent density functional theory calculations showed the similarity of the electronic features associated with R-C^C* (R = CN, COEt) and their difference with respect to R-C^C* (R-C = Naph). All of the compounds are very efficient blue emitters in poly(methyl methacrylate) films under an argon atmosphere, with QY values ranging from 68% (2B) to 93% (2C). In the solid state, the color of the emission changes to yellowish-orange for compounds 2A (λ = 600 nm) and 3C (λ = 590 nm) because of the formation of aggregates through intermolecular π···π interactions. 2C and 3C were chosen to fabricate fully solution-processed electroluminescent devices with blue-light (2C), yellow-orange-light (3C), and white-light (mixtures of 2C and 3C) emission from neat films of the compounds as emitting layers.
URIhttp://hdl.handle.net/10261/155838
DOI10.1021/acs.inorgchem.6b02826
Identificadoresdoi: 10.1021/acs.inorgchem.6b02826
e-issn: 1520-510X
issn: 0020-1669
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