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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2019, 58, 11, 7393-7408
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Isomers of Coumarin-Based Cyclometalated Ir(III) Complexes with Easily Tuned Phosphorescent Color and Features for Highly Efficient Organic Light-Emitting Diodes

  • Zhao Feng
    Zhao Feng
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    More by Zhao Feng
  • , 
  • Yue Yu
    Yue Yu
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    School of Physics and Optoelectronic Engineering, Xidian University, Xi’an 710071, PR China
    More by Yue Yu
    Orcidhttp://orcid.org/0000-0002-4758-8492
  • , 
  • Xiaolong Yang
    Xiaolong Yang
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    More by Xiaolong Yang
    Orcidhttp://orcid.org/0000-0002-0243-6698
  • , 
  • Daokun Zhong
    Daokun Zhong
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    More by Daokun Zhong
  • , 
  • Dongdong Song
    Dongdong Song
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    More by Dongdong Song
  • , 
  • Hua Yang
    Hua Yang
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    More by Hua Yang
  • , 
  • Xi Chen
    Xi Chen
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    More by Xi Chen
  • , 
  • Guijiang Zhou*
    Guijiang Zhou
    MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
    *E-mail: [email protected] (G.Z.).
    More by Guijiang Zhou
    Orcidhttp://orcid.org/0000-0002-5863-3551
  • , and 
  • Zhaoxin Wu*
    Zhaoxin Wu
    Key Laboratory of Photonics Technology for Information, School of Electronic and Information Engineering, Xi’an Jiaotong University, Xi’an 710049, PR China
    Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan 030006, PR China
    *E-mail: [email protected] (X.W.).
    More by Zhaoxin Wu
    Orcidhttp://orcid.org/0000-0003-2979-3051
Cite this: Inorg. Chem. 2019, 58, 11, 7393–7408
Publication Date (Web):May 16, 2019
https://doi.org/10.1021/acs.inorgchem.9b00534
Copyright © 2019 American Chemical Society
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    Abstract

    Abstract Image

    Three Ir(C∧N)2(acac)-type and one Ir(C1∧N)(C2∧N)(acac)-type coumarin-based cyclometalated Ir(III) complex isomers (IrC5, IrC7, IrC7-A, and IrC8) have been obtained using three coumarin-based isomers of 2-phenylpyridine (ppy)-type cyclometalating ligands (L-C5, L-C7, and L-C8). Two coordination isomers emerging as principal products (IrC7 and IrC7-A) are obtained in the synthesis of corresponding coumarin-based cyclometalated Ir(III) complexes because of two different coordination sites in ligand L-C7 to form a C–Ir bond. To the best of our knowledge, there are no such isomers reported to date. Interestingly, a broad range of phosphorescent color tuning from green (IrC8, λ = 516 nm) to red (IrC5, λ = 608 nm) has been realized through variation of the pyridyl substitution positions on the fused phenyl ring of the coumarin skeleton. In addition, based on natural transition orbital (NTO) analyses, features of the lowest triplet excited states (T1) from these coumarin-based cyclometalated Ir(III) complex isomers can be tuned easily by these ligand isomers as well. IrC5, IrC7, and IrC7-A show prevailing 3MLCT character associated with their T1 states which emit the phosphorescent signals, while the T1 state of IrC8 exhibits the dominant ligand-centered π–π* transition feature. Importantly, owing to the strong rigidity of the coumarin skeleton, all the coumarin-based cyclometalated Ir(III) complex isomers can show high phosphorescent quantum yields Φp (ca. 0.4–1). Together with the improved electron-injection/electron-transport (EI/ET) ability, all the phosphorescent emitters display impressive electroluminescence (EL) performance. The device based on IrC8 gives the highest EL efficiencies of external quantum efficiency (ηext) 22.7%, current efficiency (ηL) 79.7 cd A–1, and power efficiency (ηP) 58.2 lm W–1, representing the most state-of-the-art EL ability ever achieved by coumarin-based phosphorescent emitters. All these encouraging data definitely suggest the great potential of the coumarin skeleton in both easy tuning of the photophysical properties of ppy-type Ir(III) phosphorescent complexes and developing high-performance phosphorescent emitters.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00534.

    • Selected structural data of X-ray crystallographic results for IrC5, IrC7, and IrC7-A; HPLC spectra for IrC7 and IrC7-A; optimized S0 geometry of the third isomer IrC7-B by DFT and molecular orbital pattern of IrC8; 1H and 13C NMR spectra for all the final Ir(III) complex isomers; TGA and CV traces of these ppy-type coumarin-based cyclometalated Ir(III) complex isomers; photophysical properties at 77 or 293 K in degassed CH2Cl2 solution as well as in CBP films at 293 K for all the final Ir(III) complex isomers; contribution percentages of different segments to MOs for all the obtained Ir(III) complex isomers; contribution percentages of electron density on the chelating carbon atom to the HOMOs for all the final ligands; EL characteristics for the devices except the optimized ones (PDF)

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    CCDC 1866014–1866016 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

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