165896 20260115140312.0 doi 10.1021/acs.inorgchem.5c04705 sideral 147426 ART-2026-147426 eng Martín-Escura, Cristina Addition of Amine-Substituted Heteroaromatic Rings to Alkynyl Bridging Ligands to Generate Phosphorescent Emitters Incorporating Iridaimidazoles with Fused Heterocyclic Rings 2026 Alkynyl ligands are versatile building blocks in the design of luminescent iridium(III) complexes due to their ability to support postcoordination functionalization that gives rise to ligands non available through conventional coordination chemistry. Here, we report the synthesis and characterization of a new family of heteroleptic iridium(III) green emitters based on cyclometalated 2-p-tolylpyridine as main ligands and new C,N-chelating units as the auxiliary ligand that yield iridaimidazole structures. The alkynyl bridging dimer cis-[Ir(μ-C≡CtBu){κ2-C,N-(MeC6H3-py)}2]2 (1) reacts with amine-substituted five-membered heterocycles bearing two heteroatoms, such as 1-methyl-1H-imidazol-2-amine, 1-methyl-1H-benzo[d]imidazol-2-amine, 4-methyloxazol-2-amine, benzo[d]oxazol-2-amine, 4-methylthiazol-2-amine, and benzo[d]thiazol-2-amine, giving the iridaimidazole derivatives Ir{κ2-C,N-(MeC6H3-py)}2{κ2-C,N-[C(CH2tBu)N-im]} (im = imidazole, 2), Ir{κ2-C,N-(MeC6H3-py)}2{κ2-C,N-[C(CH2tBu)N-bzim]} (bzim = benzimidazole, 3), Ir{κ2-C,N-(MeC6H3-py)}2{κ2-C,N-[C(CH2tBu)N-oxazol]} (4), Ir{κ2-C,N-(MeC6H3-py)}2{κ2-C,N-[C(CH2tBu)N-bzoxazol]} (5), Ir{κ2-C,N-(MeC6H3-py)}2{κ2-C,N-[C(CH2tBu)N-thiazol]} (6), and Ir{κ2-C,N-(MeC6H3-py)}2{κ2-C,N-[C(CH2tBu)N-bzthiazol]} (7), respectively. The iridium center in these complexes is in an octahedral environment with nitrogen and carbon atoms in a facial disposition. Complexes 2, 4, and 6 feature one five-membered heteroaromatic ring fused to the iridaimidazole cycle whereas 3, 5, and 7 additionally contain a benzo group fused to the organic heterocycle. All complexes are green phosphorescent emitters (474–558 nm) upon photoexcitation, with high quantum yields (0.55–0.92) in poly(methyl methacrylate) films and 2-MeTHF at 298 K. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/AEI/PID2023-146967NB-I00 info:eu-repo/grantAgreement/ES/DGA/E06-23R info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Oñate, Enrique (orcid)0000-0003-2094-719X Oliván, Montserrat (orcid)0000-0003-0381-0917 López, Ana M. Universidad de Zaragoza (orcid)0000-0001-7183-4975 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 65, 1 (2026), 582-592 Inorg. chem. Inorganic Chemistry 0020-1669 3850456 http://zaguan.unizar.es/record/165896/files/texto_completo.pdf Versión publicada 3120917 http://zaguan.unizar.es/record/165896/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:165896 articulos driver 2026-01-15-12:37:29 ARTICLE