2024-03-29T08:58:09Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/2226672021-10-16T04:32:23Zcom_10261_52707com_10261_5col_10261_52708
Insertion of unsaturated C–C Bonds into the O–H bond of an Iridium(III)-Hydroxo complex: formation of phosphorescent emitters with an asymmetrical β-Diketonate ligand
Boudreault, Pierre-Luc T.
Esteruelas, Miguel A.
López, Ana M.
Oñate, Enrique
Raga, Esther
Tsai, Jui-Yi
Gobierno de Aragón
European Commission
Ministerio de Ciencia, Innovación y Universidades (España)
A synthetic methodology to prepare iridium(III) emitters of the class [3b+3b+3b′] with two ortho-metalated 1-phenylisoquinolines and an asymmetrical β-diketonate has been discovered. The abstraction of the chloride ligands of the dimer [Ir(μ-Cl){κ2-C,N-(C6H4-isoqui)}2]2 (1, C6H5-isoqui = 1-phenylisoquinoline) with AgBF4 in acetone and the subsequent addition of water to the resulting solution affords the water solvate mononuclear complex [Ir{κ2-C,N-(C6H4-isoqui)}2(H2O)2]BF4 (2), which reacts with KOH to give the dihydroxo-bridged dimer [Ir(μ-OH){κ2-C,N-(C6H4-isoqui)}2]2 (3). Treatment of the latter with dimethyl acetylenedicarboxylate leads to Ir{κ2-C,N-(C6H4-isoqui)}2{κ2-O,O-[OC(CO2CH3)CHC(OCH3)O]} (4), as a result of the anti-addition of the O–H bond of a mononuclear [Ir(OH){κ2-C,N-(C6H4-isoqui)}2] fragment to the C–C triple bond of the alkyne and the coordination of one of the carboxylate substituents to the metal center. Complex 3 also reacts with α,β-unsaturated ketones. The reaction with 3-(4-methylphenyl)-1-phenylprop-2-en-1-one affords Ir{κ2-C,N-(C6H4-isoqui)}2{κ2-O,O-[OC(C6H5)CHC(p-C6H4Me)O]} (5), whereas methyl vinyl ketone gives a mixture of Ir{κ2-C,N-(C6H4-isoqui)}2{κ2-O,O-[OC(CH3)CHCHO]} (6) and Ir{κ2-C,N-(C6H4-isoqui)}2{κ2-O,O-[OC(CH3)CHC(CH═CH2)O]} (7). Complexes 5 and 6 are the result of the addition of the O–H bond of the mononuclear [Ir(OH){κ2-C,N-(C6H4-isoqui)}2] fragment to the C–C double bond of the α,β-unsaturated ketones and the coordination of the carbonyl group to the iridium center, to generate O,O-chelates which lose molecular hydrogen to aromatize into the asymmetrical β-diketonate ligands. Complexes 4–7 are phosphorescent emitters in the red spectral region (599–672 nm) in doped poly(methyl methacrylate) (PMMA) film at 5 wt % at room temperature and 2-methyltetrahydrofuran at room temperature and 77 K. They display short lifetimes (0.8–2.5 μs) and quantum yields in both doped PMMA films and in 2-methyltetrahydrofuran at room temperature depending on the substituents of the β-diketonate: about 0.6–0.5 for 4 and 6 and ca. 0.35 for 5 and 7.
2020-11-11T08:03:12Z
2020-11-11T08:03:12Z
2020-10-15
artículo
Inorganic Chemistry 59 (21): 15877-15887 (2020)
0020-1669
http://hdl.handle.net/10261/222667
10.1021/acs.inorgchem.0c02395
1520-510X
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100010067
eng
Postprint
https://doi.org/10.1021/acs.inorgchem.0c02395
Sí
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-82935-P
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102387-T
openAccess
American Chemical Society