000165801 001__ 165801
000165801 005__ 20260114135812.0
000165801 0247_ $$2doi$$a10.1021/acs.inorgchem.2c03522
000165801 0248_ $$2sideral$$a131677
000165801 037__ $$aART-2022-131677
000165801 041__ $$aeng
000165801 100__ $$aBenítez, María$$uUniversidad de Zaragoza
000165801 245__ $$aAcetylides for the preparation of phosphorescent iridium(iii) complexes: iridaoxazoles and their transformation into hydroxycarbenes and N,C(sp3),C(sp2),O-Tetradentate ligands
000165801 260__ $$c2022
000165801 5060_ $$aAccess copy available to the general public$$fUnrestricted
000165801 5203_ $$aThe preparation of three families of phosphorescent iridium(III) emitters, including iridaoxazole derivatives, hydroxycarbene compounds, and N,C(sp3),C(sp2),O-tetradentate containing complexes, has been performed starting from dimers cis-[Ir(μ2-η2-C≡CR){κ2-C,N-(MeC6H3-py)}2]2 (R = tBu (1a), Ph (1b)). Reactions of 1a with benzamide, acetamide, phenylacetamide, and trifluoroacetamide lead to the iridaoxazole derivatives Ir{κ2-C,O-[C(CH2tBu)NC(R)O]}{κ2-C,N-(MeC6H3-py)}2 (R = Ph (2), Me (3), CH2Ph (4), CF3 (5)) with a fac disposition of carbons and heteroatoms around the metal center. In 2-methyltetrahydrofuran and dichloromethane, water promotes the C–N rupture of the IrC–N bond of the iridaoxazole ring of 3–5 to form amidate–iridium(III)–hydroxycarbene derivatives Ir{κ1-N-[NHC(R)O]}{κ2-C,N-(MeC6H3-py)}2{═C(CH2tBu)OH} (R = Me (6), CH2Ph (7), CF3 (8)). In contrast to 1a, dimer 1b reacts with benzamide and acetamide to give Ir{κ4-N,C,C′,O-[py-MeC6H3-C(CH2-C6H4)NHC(R)O]}{κ2-C,N-(MeC6H3-py)}(R = Ph (9), Me (10)), which bear a N,C(sp3),C(sp2),O-tetradentate ligand resulting from a triple coupling (an alkynyl ligand, an amide, and a coordinated aryl group) and a C–H bond activation at the metal coordination sphere. Complexes 2–4 and 6–10 are emissive upon photoexcitation, in orange (2–4), green (6–8), and yellow (9 and 10) regions, with quantum yields between low and moderate (0.01–0.50) and short lifetimes (0.2–9.0 μs).
000165801 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9fo:eu-repo/grantAgreement/ES/DGA-FSE/LMP23-21$$9info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MICINN/RED2018-102387-T
000165801 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000165801 590__ $$a4.6$$b2022
000165801 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 42 = 0.119$$c2022$$dQ1$$eT1
000165801 592__ $$a0.997$$b2022
000165801 593__ $$aChemistry (miscellaneous)$$c2022$$dQ1
000165801 593__ $$aPhysical and Theoretical Chemistry$$c2022$$dQ1
000165801 593__ $$aInorganic Chemistry$$c2022$$dQ1
000165801 594__ $$a8.0$$b2022
000165801 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000165801 700__ $$0(orcid)0000-0002-3284-1053$$aBuil, María L.$$uUniversidad de Zaragoza
000165801 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.
000165801 700__ $$0(orcid)0000-0002-6608-1910$$aIzquierdo, Susana$$uUniversidad de Zaragoza
000165801 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000165801 700__ $$aTsai, Jui-Yi
000165801 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000165801 773__ $$g61, 48 (2022), 19597-19611$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000165801 8564_ $$s4135225$$uhttps://zaguan.unizar.es/record/165801/files/texto_completo.pdf$$yVersión publicada
000165801 8564_ $$s3037539$$uhttps://zaguan.unizar.es/record/165801/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000165801 909CO $$ooai:zaguan.unizar.es:165801$$particulos$$pdriver
000165801 951__ $$a2026-01-14-12:46:04
000165801 980__ $$aARTICLE