Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand

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-pheny...

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Autores: Adamovich, Vadim, Bajo, Sonia, Boudreault, Pierre-Luc T., Esteruelas, Miguel Ángel, López, Ana M., Martín, Jaime, Oliván, Montserrat, Oñate, Enrique, Palacios, Adrián U., San-Torcuato Sanz, Ainhoa, Tsai, Jui-Yi, Xia, Chuanjun
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2018
País:España
Recursos:Universidad de Zaragoza
Repositório:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:79778
Acesso em linha:http://zaguan.unizar.es/record/79778
Access Level:Acceso aberto
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spelling Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene LigandAdamovich, VadimBajo, SoniaBoudreault, Pierre-Luc T.Esteruelas, Miguel ÁngelLópez, Ana M.Martín, JaimeOliván, MontserratOñate, EnriquePalacios, Adrián U.San-Torcuato Sanz, AinhoaTsai, Jui-YiXia, ChuanjunA 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.2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://zaguan.unizar.es/record/79778reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA/E06-17Rinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDCinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-Pinfo:eu-repo/semantics/openAccessoai:zaguan.unizar.es:797782026-05-29T13:59:51Z
dc.title.none.fl_str_mv Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
title Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
spellingShingle Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
Adamovich, Vadim
title_short Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
title_full Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
title_fullStr Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
title_full_unstemmed Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
title_sort Preparation of Tris-Heteroleptic Iridium(III) Complexes Containing a Cyclometalated Aryl-N-Heterocyclic Carbene Ligand
dc.creator.none.fl_str_mv Adamovich, Vadim
Bajo, Sonia
Boudreault, Pierre-Luc T.
Esteruelas, Miguel Ángel
López, Ana M.
Martín, Jaime
Oliván, Montserrat
Oñate, Enrique
Palacios, Adrián U.
San-Torcuato Sanz, Ainhoa
Tsai, Jui-Yi
Xia, Chuanjun
author Adamovich, Vadim
author_facet Adamovich, Vadim
Bajo, Sonia
Boudreault, Pierre-Luc T.
Esteruelas, Miguel Ángel
López, Ana M.
Martín, Jaime
Oliván, Montserrat
Oñate, Enrique
Palacios, Adrián U.
San-Torcuato Sanz, Ainhoa
Tsai, Jui-Yi
Xia, Chuanjun
author_role author
author2 Bajo, Sonia
Boudreault, Pierre-Luc T.
Esteruelas, Miguel Ángel
López, Ana M.
Martín, Jaime
Oliván, Montserrat
Oñate, Enrique
Palacios, Adrián U.
San-Torcuato Sanz, Ainhoa
Tsai, Jui-Yi
Xia, Chuanjun
author2_role author
author
author
author
author
author
author
author
author
author
author
description 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.
publishDate 2018
dc.date.none.fl_str_mv 2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
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status_str acceptedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/79778
url http://zaguan.unizar.es/record/79778
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv 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
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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