79778 20200117221607.0 doi 10.1021/acs.inorgchem.8b01367 sideral 107818 ART-2018-107818 eng Adamovich, Vadim Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand 2018 Access copy available to the general public Unrestricted A new class of phosphorescent tris-heteroleptic iridium(III) complexes has been discovered. The addition of PhMeImAgI (PhMeIm = 1-phenyl-3-methylimidazolylidene) to the dimer [Ir(µ-Cl)(COD)]2 (1; COD = 1,5-cyclooctadiene) affords IrCl(COD)(PhMeIm) (2), which reacts with 1-phenylisoquinoline, 2-phenylpyridine, and 2-(2,4-difluorophenyl)pyridine to give the respective dimers [Ir(µ-Cl){¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6H4-isoqui)}]2 (3), [Ir(µ-Cl){¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6H4-py)}]2 (4), and [Ir(µ-Cl){¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6F2H2-py)}]2 (5), as a result of the N-heterocyclic carbene (NHC)- and N-heterocycle-supported o-CH bond activation of the aryl substituents and the hydrogenation of a C–C double bond of the coordinated diene. In solution, these dimers exist as a mixture of isomers a (Im trans to N) and b (Im trans to Cl), which lie in a dynamic equilibrium. The treatment of 3–5 with Kacac (acac = acetylacetonate) yields isomers a (Im trans to N) and b (Im trans to O) of Ir{¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6H4-isoqui)}(¿2-O,O-acac) (6a and 6b), Ir{¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6H4-py)}(¿2-O,O-acac) (7a and 7b), and Ir{¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6F2H4-py)}(¿2-O,O-acac) (8a and 8b), which were separated by column chromatography. The treatment of 6a with HX in acetone–water produces the protonation of the acac ligand and the formation of the bis(aquo) complex [Ir{¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6H4-isoqui)}(H2O)2]X [X = BF4 (9a[BF4]), OTf (9a[OTf])]. The salt 9a[BF4] reacts with 2-(2-pinacolborylphenyl)-5-methylpyridine in the presence of 40 equiv of K3PO4 to afford Ir{¿2-C,C-(C6H4-ImMe)}{¿2-C,N-(C6H4-isoqui)}{¿2-C,N-(C6H4-Mepy)} (10a). Complexes 6a, 6b, 7a, 7b, 8a, 8b, and 10a are phosphorescent emitters (¿em = 465–655 nm), which display short lifetimes in the range of 0.2–5.6 µs. They show high quantum yields both in doped poly(methyl methacrylate) films (0.34–0.87) and in 2-methyltetrahydrofuran at room temperature (0.40–0.93). From the point of view of their applicability to the fabrication of organic-light-emitting-diode devices, a notable improvement with regard to those containing two cyclometalated C,N ligands is achieved. The introduction of the cyclometalated aryl-NHC group allows one to reach a brightness of 1000 cd/m2 at a lower voltage and appears to give rise to higher luminous efficacy and power efficacy. info:eu-repo/grantAgreement/ES/DGA/E06-17R info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.85 2018 CHEMISTRY, INORGANIC & NUCLEAR 4 / 45 = 0.089 2018 Q1 T1 1.501 2018 Chemistry (miscellaneous) 2018 Q1 Physical and Theoretical Chemistry 2018 Q1 Inorganic Chemistry 2018 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion (orcid)0000-0003-4803-566X Bajo, Sonia Boudreault, Pierre-Luc T. (orcid)0000-0002-4829-7590 Esteruelas, Miguel Ángel (orcid)0000-0001-7183-4975 López, Ana M. Universidad de Zaragoza (orcid)0000-0003-0909-3509 Martín, Jaime Universidad de Zaragoza (orcid)0000-0003-0381-0917 Oliván, Montserrat (orcid)0000-0003-2094-719X Oñate, Enrique (orcid)0000-0003-2838-9102 Palacios, Adrián U. (orcid)0000-0003-1709-3672 San-Torcuato Sanz, Ainhoa Tsai, Jui-Yi Xia, Chuanjun 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 57, 17 (2018), 10744-10760 Inorg. chem. Inorganic Chemistry 0020-1669 914161 http://zaguan.unizar.es/record/79778/files/texto_completo.pdf Postprint 50310 http://zaguan.unizar.es/record/79778/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:79778 articulos driver 2020-01-17-21:47:01 ARTICLE