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Non-Stereogenic Dinuclear Ir(III) Complex with a Molecular Rack Design to Afford Efficient Thermally Enhanced Red Emission

  • Marsel Z. Shafikov*
    Marsel Z. Shafikov
    Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Universitätsstrasse 31, Regensburg 93053, Germany
    Ural Federal University, Mira 19, Ekaterinburg 620002, Russia
    *Email: [email protected]
  • Ross Martinscroft
    Ross Martinscroft
    Department of Applied Sciences, Northumbria University, Newcastle upon Tyne NE1 8ST, United Kingdom
  • Craig Hodgson
    Craig Hodgson
    Department of Applied Sciences, Northumbria University, Newcastle upon Tyne NE1 8ST, United Kingdom
  • Anna Hayer
    Anna Hayer
    Merck KGaA, Frankfurter Str. 250, 64293 Darmstadt, Germany
    More by Anna Hayer
  • Armin Auch
    Armin Auch
    Merck KGaA, Frankfurter Str. 250, 64293 Darmstadt, Germany
    More by Armin Auch
  • , and 
  • Valery N. Kozhevnikov*
    Valery N. Kozhevnikov
    Department of Applied Sciences, Northumbria University, Newcastle upon Tyne NE1 8ST, United Kingdom
    *Email: [email protected]
Cite this: Inorg. Chem. 2021, 60, 3, 1780–1789
Publication Date (Web):January 20, 2021
https://doi.org/10.1021/acs.inorgchem.0c03251
Copyright © 2021 American Chemical Society
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Abstract

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Cyclometalated complexes containing two or more metal centers were recently shown to offer photophysical properties that are advantageous compared to their mononuclear analogues. Here we report the design, synthesis, and luminescent properties of a dinuclear Ir(III) complex formed by a ditopic N^C^N–N^C^N bridging ligand (L1) with pyrimidine as a linking heterocycle. Two dianionic C^N^C terminal ligands were employed to achieve a charge-neutral and nonstereogenic dinuclear complex 5. This complex shows a highly efficient red emission with a maximum at λem = 642 nm as measured for a toluene solution. The decay time and emission quantum yield of the complex measured for the degassed sample are τ = 1.31 μs and ΦPL = 80%, respectively, corresponding to the radiative rate of kr = 6.11·105 s–1. This rate value is approximately fourfold faster than for the green-emitting mononuclear analogue 3. Cryogenic temperature measurements show that the three substrates of the lowest triplet state T1 of 5 emit with decay times of τ(I) = 120 μs, τ(II) = 7 μs, and τ(III) = 1 μs that are much shorter compared to those of the mononuclear complex 3, which has values of τ(I) = 192 μs, τ(II) = 65.6 μs, and τ(III) = 3.6 μs. These data indicate that the spin–orbit coupling of state T1 with the singlet states is much stronger in the case of complex 5, which results in a much higher T1 → S0 emission rate. Indeed, a computational analysis suggests that in the dinuclear complex 5 the T1 state is spin–orbit coupled with twice the number of singlet states compared to that of mononuclear 3, which is a result of the electronic coupling of two coordination sites. The investigation of the temperature dependence of the emission rates of 3 and 5 shows that the room-temperature emission of both complexes is mainly contributed by a thermally populated excited state lying above the T1 state. To the best of our knowledge, complexes 3 and 5 are the first examples of Ir(III) complexes that show photophysical behavior reminiscent of thermally activated delayed fluorescence (TADF).

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03251.

  • Experimental information; synthetic procedures for the synthesis of all compounds; 1H NMR characterization and mass spectrometric and elemental analysis data for 3, 5, and intermediates; crystallographic data, TD-DFT-calculated absorption spectra, further output data, and DFT-optimized geometries for model complexes 3′ and 5′ (PDF)

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CCDC 19766401976641 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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Cited By


This article is cited by 13 publications.

  1. Ze-Rong Ge, Xin Tong, Yi-Chuan Huang, Wen-Hao Li, Hong-Yan Li, Ai-Dang Lu, Tian-Yi Li. Highly Luminescent Dinuclear Iridium(III) Complexes Containing Phenanthroline-Based Neutral Ligands as Chemosensors for Cu2+ Ion. Organometallics 2022, 41 (6) , 706-715. https://doi.org/10.1021/acs.organomet.1c00617
  2. Zhong Zheng, Ze-Lin Zhu, Cheuk-Lam Ho, Shek-Man Yiu, Chun-Sing Lee, Songwut Suramitr, Supa Hannongbua, Yun Chi. Stepwise Access of Emissive Ir(III) Complexes Bearing a Multi-Dentate Heteroaromatic Chelate: Fundamentals and Applications. Inorganic Chemistry 2022, 61 (10) , 4384-4393. https://doi.org/10.1021/acs.inorgchem.1c03794
  3. Marsel Z. Shafikov, Andrey V. Zaytsev, Valery N. Kozhevnikov. Cyclometalation Geometry of the Bridging Ligand as a Tuning Tool for Photophysics of Dinuclear Ir(III) Complexes. The Journal of Physical Chemistry C 2021, 125 (37) , 20531-20537. https://doi.org/10.1021/acs.jpcc.1c05037
  4. Marsel Z. Shafikov, Alfiya F. Suleymanova, Roger J. Kutta, Alexander Gorski, Aleksandra Kowalczyk, Magdalena Gapińska, Konrad Kowalski, Rafał Czerwieniec. Ligand design and nuclearity variation towards dual emissive Pt( ii ) complexes for singlet oxygen generation, dual channel bioimaging, and theranostics. Journal of Materials Chemistry C 2022, 10 (14) , 5636-5647. https://doi.org/10.1039/D2TC00257D
  5. Sylvain Achelle, Maxime Hodée, Julien Massue, Arnaud Fihey, Claudine Katan. Diazine-based thermally activated delayed fluorescence chromophores. Dyes and Pigments 2022, 200 , 110157. https://doi.org/10.1016/j.dyepig.2022.110157
  6. Piotr Pander, Andrey V. Zaytsev, Amit Sil, J. A. Gareth Williams, Valery N. Kozhevnikov, Fernando B. Dias. Enhancement of thermally activated delayed fluorescence properties by substitution of ancillary halogen in a multiple resonance-like diplatinum( ii ) complex. Journal of Materials Chemistry C 2022, 10 (12) , 4851-4860. https://doi.org/10.1039/D1TC05026E
  7. Marsel Z. Shafikov, Craig Hodgson, Aleksander Gorski, Aleksandra Kowalczyk, Magdalena Gapińska, Konrad Kowalski, Rafał Czerwieniec, Valery N. Kozhevnikov. Benzannulation of a ditopic ligand to afford mononuclear and dinuclear Ir( iii ) complexes with intense phosphorescence: applications in singlet oxygen generation and bioimaging. Journal of Materials Chemistry C 2022, 10 (5) , 1870-1877. https://doi.org/10.1039/D1TC05271C
  8. Matías Vidal, José Rodríguez‐Aguilar, Ignacio Aburto, Carolina Aliaga, Moisés Domínguez. Reactivity of 4‐pyrimidyl Sulfonic Esters in Suzuki‐Miyaura Cross‐Coupling Reactions in Water Under Microwave Irradiation. ChemistrySelect 2021, 6 (45) , 12858-12861. https://doi.org/10.1002/slct.202103280
  9. Stanislav Bezzubov, Kirill Ermolov, Alexander Gorbunov, Paulina Kalle, Ivan Lentin, Gennadij Latyshev, Vladimir Kovalev, Ivan Vatsouro. Inherently dinuclear iridium( iii ) meso architectures accessed by cyclometalation of calix[4]arene-based bis(aryltriazoles). Dalton Transactions 2021, 50 (45) , 16765-16769. https://doi.org/10.1039/D1DT03579G
  10. Jie Yan, Ze-Lin Zhu, Chun-Sing Lee, Shih-Hung Liu, Pi-Tai Chou, Yun Chi. Probing Electron Excitation Characters of Carboline-Based Bis-Tridentate Ir(III) Complexes. Molecules 2021, 26 (19) , 6048. https://doi.org/10.3390/molecules26196048
  11. Piotr Pander, Andrey V. Zaytsev, Amit Sil, J. A. Gareth Williams, Pierre-Henri Lanoe, Valery N. Kozhevnikov, Fernando B. Dias. The role of dinuclearity in promoting thermally activated delayed fluorescence (TADF) in cyclometallated, N^C^N-coordinated platinum( ii ) complexes. Journal of Materials Chemistry C 2021, 9 (32) , 10276-10287. https://doi.org/10.1039/D1TC02562G
  12. Ying Zhou, Yao Li, Rong Zhang, Dahui Zhao, Qifan Yan. White Light Luminescence from a Homo‐conjugated Molecule with Thermally Activated Delayed Fluorescence. Chemistry – An Asian Journal 2021, 16 (14) , 1893-1896. https://doi.org/10.1002/asia.202100397
  13. Matteo Mauro. Phosphorescent multinuclear complexes for optoelectronics: tuning of the excited-state dynamics. Chemical Communications 2021, 57 (48) , 5857-5870. https://doi.org/10.1039/D1CC01077H

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