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    Highly Emissive Dinuclear Platinum(III) Complexes
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    • Xiugang Wu
      Xiugang Wu
      School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications, Jiangsu Key Laboratories of Environment-Friendly Polymers, National Experimental Demonstration Center for Materials Science and Engineering, Changzhou University, Changzhou 213164, China
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    • Deng-Gao Chen
      Deng-Gao Chen
      Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
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      Orcidhttp://orcid.org/0000-0001-6406-2209
    • Denghui Liu
      Denghui Liu
      School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications, Jiangsu Key Laboratories of Environment-Friendly Polymers, National Experimental Demonstration Center for Materials Science and Engineering, Changzhou University, Changzhou 213164, China
      More by Denghui Liu
    • Shih-Hung Liu
      Shih-Hung Liu
      Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
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    • Shin-Wei Shen
      Shin-Wei Shen
      Graduate Institute of Photonics and Optoelectronics, National Taiwan University, Taipei 10617, Taiwan
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    • Chih-I Wu
      Chih-I Wu
      Graduate Institute of Photonics and Optoelectronics, National Taiwan University, Taipei 10617, Taiwan
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      Orcidhttp://orcid.org/0000-0003-3613-7511
    • Guohua Xie
      Guohua Xie
      Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, Department of Chemistry, Wuhan University, Wuhan 430072, China
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      Orcidhttp://orcid.org/0000-0003-0764-7889
    • Jianwei Zhou
      Jianwei Zhou
      School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications, Jiangsu Key Laboratories of Environment-Friendly Polymers, National Experimental Demonstration Center for Materials Science and Engineering, Changzhou University, Changzhou 213164, China
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    • Zhi-Xuan Huang
      Zhi-Xuan Huang
      Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
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    • Chun-Ying Huang
      Chun-Ying Huang
      Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
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      Orcidhttp://orcid.org/0000-0001-6757-113X
    • Shi-Jian Su
      Shi-Jian Su
      Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640, China
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      Orcidhttp://orcid.org/0000-0002-6545-9002
    • Weiguo Zhu*
      Weiguo Zhu
      School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications, Jiangsu Key Laboratories of Environment-Friendly Polymers, National Experimental Demonstration Center for Materials Science and Engineering, Changzhou University, Changzhou 213164, China
      *[email protected]
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      Orcidhttp://orcid.org/0000-0002-4244-2638
    • Pi-Tai Chou*
      Pi-Tai Chou
      Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
      *[email protected]
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      Orcidhttp://orcid.org/0000-0002-8925-7747
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 16, 7469–7479
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    https://doi.org/10.1021/jacs.9b13956
    Published March 29, 2020
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    Abstract

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    Dinuclear Pt(III) complexes were commonly reported to have short-lived lowest-lying triplet states, resulting in extremely weak or no photoluminescence. To overcome this obstacle, a new series of dinuclear Pt(III) complexes, named Pt2a-Pt2c, were strategically designed and synthesized using donor (D)–acceptor (A)-type oxadiazole-thiol chelates as bridging ligands. These dinuclear Pt(III) complexes possess a d7–d7 electronic configuration and exhibit intense phosphorescence under ambient conditions. Among them, Pt2a exhibits orange phosphorescence maximized at 618 nm in degassed dichloromethane solution (Φp ≈ 8.2%, τp ≈ 0.10 μs) and near-infrared (NIR) emission at 749 nm (Φp ≈ 10.1% τp ≈ 0.66 μs) in the crystalline powder and at 704 nm (Φp ≈ 33.1%, τp ≈ 0.34 μs) in the spin-coated neat film. An emission blue-shifted by more than 3343 cm–1 is observed under mechanically ground crystalline Pt2a, affirming intermolecular interactions in the solid states. Time-dependent density functional theory (TD-DFT) discloses the lowest-lying electronic transition of Pt2a-Pt2c complexes to be a bridging ligand–metal–metal charge transfer (LMMCT) transition. The long-lived triplet states of these dinuclear platinum(III) complexes may find potential use in lighting. Employing Pt2a as an emitter, high-performance organic light-emitting diodes (OLEDs) were fabricated with NIR emission at 716 nm (η = 5.1%), red emission at 614 nm (η = 8.7%), and white-light emission (η = 11.6%) in nondoped, doped (in mCP), and hybrid (in CzACSF) devices, respectively.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.9b13956.

    • General information, syntheses, analytical data, DFT studies, photophysical studies, thermal studies, electrochemical studies, and EL data (PDF)

    • Crystallographic data of Pt2a (CIF)

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