000079778 001__ 79778
000079778 005__ 20200117221607.0
000079778 0247_ $$2doi$$a10.1021/acs.inorgchem.8b01367
000079778 0248_ $$2sideral$$a107818
000079778 037__ $$aART-2018-107818
000079778 041__ $$aeng
000079778 100__ $$aAdamovich, Vadim
000079778 245__ $$aPreparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
000079778 260__ $$c2018
000079778 5060_ $$aAccess copy available to the general public$$fUnrestricted
000079778 5203_ $$aA 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.
000079778 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-17R$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P
000079778 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000079778 590__ $$a4.85$$b2018
000079778 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b4 / 45 = 0.089$$c2018$$dQ1$$eT1
000079778 592__ $$a1.501$$b2018
000079778 593__ $$aChemistry (miscellaneous)$$c2018$$dQ1
000079778 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000079778 593__ $$aInorganic Chemistry$$c2018$$dQ1
000079778 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000079778 700__ $$0(orcid)0000-0003-4803-566X$$aBajo, Sonia
000079778 700__ $$aBoudreault, Pierre-Luc T.
000079778 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel Ángel
000079778 700__ $$0(orcid)0000-0001-7183-4975$$aLópez, Ana M.$$uUniversidad de Zaragoza
000079778 700__ $$0(orcid)0000-0003-0909-3509$$aMartín, Jaime$$uUniversidad de Zaragoza
000079778 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, Montserrat
000079778 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000079778 700__ $$0(orcid)0000-0003-2838-9102$$aPalacios, Adrián U.
000079778 700__ $$0(orcid)0000-0003-1709-3672$$aSan-Torcuato Sanz, Ainhoa
000079778 700__ $$aTsai, Jui-Yi
000079778 700__ $$aXia, Chuanjun
000079778 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000079778 773__ $$g57, 17 (2018), 10744-10760$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000079778 8564_ $$s914161$$uhttps://zaguan.unizar.es/record/79778/files/texto_completo.pdf$$yPostprint
000079778 8564_ $$s50310$$uhttps://zaguan.unizar.es/record/79778/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000079778 909CO $$ooai:zaguan.unizar.es:79778$$particulos$$pdriver
000079778 951__ $$a2020-01-17-21:47:01
000079778 980__ $$aARTICLE