Citation: Wen-Si YU, Chun-Hua HUANG, Xi-He HUANG. Synthesis, Structure and Photophysical Properties of a Dinuclear Copper(I) Complex Based on Phosphino-pyridine and Diphosphine Mixed-ligands[J]. Chinese Journal of Structural Chemistry, ;2021, 40(2): 175-181. doi: 10.14102/j.cnki.0254–5861.2011–2788 shu

Synthesis, Structure and Photophysical Properties of a Dinuclear Copper(I) Complex Based on Phosphino-pyridine and Diphosphine Mixed-ligands

Institute of Optical Crystalline Materials, College of Chemistry, Fuzhou University, Fuzhou 350116, China

Corresponding author: Xi-He HUANG, xhhuang@fzu.edu.cn
Received Date: 26 February 2020
Accepted Date: 14 April 2020

Fund Project: the Natural Science Foundation of Fujian Province 2017J01576

Figures(5)

Treatment of bis(diphenylphosphino)methane (dppm) and 2-(diphenylphosphanyl)pyridine (dpppy) with Cu(CH₃CN)₄BF₄ afforded a dinuclear Cu(I) complex [Cu₂(dpppy)₂(dppm)(CH₃CN)](BF₄)₂·3CH₂Cl₂ (1). Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail. It crystallizes in triclinic space group P\begin{document}$ \overline 1 $\end{document} with a = 13.0834(8), b = 13.5568(8), c = 21.8544(11) Å, α = 76.090(5)°, β = 80.803(5)°, γ = 64.582(6)°, V = 3391.3(3) Å³, Z = 2, M_r = 1507.42, D_c = 1.476 g/cm³, F(000) = 1532, GOOF = 1.071, the final R = 0.0700 for 9041 observed reflections with I > 2σ(I) and wR = 0.2063 for all data. The complex contains a Cu₂-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement. In the crystalline phase, complex 1 exhibits bright bluish-green photoluminescence (λ_max = 488 nm) with high quantum yield (ϕ = 0.57) at room temperature. It is still a relatively high emission quantum yield (ϕ = 0.36) in doped PMMA thin film with 20 wt% dopant of complex 1. The emission peaks of 1 in dichloromethane solution and doped PMMA (20 wt%) thin films are 510 and 494 nm, respectively, showing a very slight bathochromic shift compared to that in crystalline phase. This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper lefts in the excited state.
- copper(I) complex,
- thermally activated delayed fluorescence,
- crystalline structure
1. [1]
  Uoyama, H.; Goushi, K.; Shizu, K.; Nomura, H.; Adachi, C. Highly efficient organic light-emitting diodes from delayed fluorescence. Nature 2012, 492, 234–238. doi: 10.1038/nature11687
2. [2]
  Bizzarri, C.; Spuling, E.; Knoll, D. M.; Volz, D.; Bräse, S. Sustainable metal complexes for organic light-emitting diodes (OLEDs). Coord. Chem. Rev. 2018, 373, 49–82. doi: 10.1016/j.ccr.2017.09.011
3. [3]
  Yang, M.; Chen, X. L.; Lu, C. Z. Efficiently luminescent copper(I) iodide complexes with crystallization-induced emission enhancement (CIEE). Dalton Trans. 2019, 48, 10790–10794. doi: 10.1039/C9DT01910C
4. [4]
  Fleetham, T.; Li, G.; Li, J. Phosphorescent Pt(Ⅱ) and Pd(Ⅱ) complexes for efficient, high-color-quality, and stable OLEDs. Adv. Mater. 2017, 29, 1601861. doi: 10.1002/adma.201601861
5. [5]
  Wu, Y.; Tan, X.; Lv, A.; Yu, F.; Ma, H.; Shen, K.; Sun, Z.; Chen, F.; Chen, Z. K.; Hang, X. C. Triplet excited-state engineering of phosphorescent Pt(Ⅱ) complexes. J. Phys. Chem. Lett. 2019, 10, 5105–5110. doi: 10.1021/acs.jpclett.9b01685
6. [6]
  Femoni, C.; Muzzioli, S.; Palazzi, A.; Stagni, S.; Zacchini, S.; Monti, F.; Accorsi, G.; Bolognesi, M.; Armaroli, N.; Massi, M.; Valenti, G.; Marcaccio, M. New tetrazole-based Cu(I) homo- and hetero-leptic complexes with various P^P ligands: synthesis, characterization, redox and photophysical properties. Dalton Trans. 2013, 42, 997–1010. doi: 10.1039/C2DT32056H
7. [7]
  Yersin, H.; Rausch, A. F.; Czerwieniec, R.; Hofbeck, T.; Fischer, T. The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs. Coord. Chem. Rev. 2011, 255, 2622–2652. doi: 10.1016/j.ccr.2011.01.042
8. [8]
  Deaton, J. C.; Switalski, S. C.; Kondakow, D. Y.; Young, R. H.; Pawlik, T. D.; Giesen, D. J.; Harkins, S. B.; Miller, A. J. M.; Mickenberg, S. F.; Peters, J. C. E-Type delayed fluorescence of a phosphine-supported Cu₂(μ-NAr₂)₂ diamond core: harvesting singlet and triplet excitons in OLEDs. J. Am. Chem. Soc. 2010, 132, 9499–9508. doi: 10.1021/ja1004575
9. [9]
  Hofbeck, T.; Monkowius, U.; Yersin, H. Highly efficient luminescence of Cu(I) compounds: thermally activated delayed fluorescence combined with short-lived phosphorescence. J. Am. Chem. Soc. 2015, 137, 399–404. doi: 10.1021/ja5109672
10. [10]
  Czerwieniec, R.; Leitl, M. J.; Homeier, H. H. H.; Yersin, H. Cu(I) complexes-thermally activated delayed fluorescence. photophysical approach and material design. Coord. Chem. Rev. 2016, 325, 2–28. doi: 10.1016/j.ccr.2016.06.016
11. [11]
  Mara, M. W.; Fransted, K. A.; Chen, L. X. Interplays of excited state structures and dynamics in copper(I) diimine complexes: implications and perspectives. Coord. Chem. Rev. 2015, 282, 2–18.
12. [12]
  Jia, J. H.; Chen, X. L.; Liao, J. Z.; Liang, D.; Yang, M. X.; Yu, R.; Lu, C. Z. Highly luminescent copper(I) halide complexes chelated with a tetradentate ligand (PNNP): synthesis, structure, photophysical properties and theoretical studies. Dalton Trans. 2019, 48, 1418–1426. doi: 10.1039/C8DT03452D
13. [13]
  Cuttell, D. G.; Kuang, S. M.; Fanwick, P. E.; McMillin, D. R.; Walton, R. A. Simple Cu(I) complexes with unprecedented excited-state lifetimes. J. Am. Chem. Soc. 2002, 124, 6–7. doi: 10.1021/ja012247h
14. [14]
  Harkins, S. B.; Peters, J. C. A highly emissive Cu₂N₂ diamond core complex supported by a [PNP]-ligand. J. Am. Chem. Soc. 2005, 127, 2030–2031. doi: 10.1021/ja043092r
15. [15]
  Schinabeck, A.; Rau, N.; Klein, M.; Sundermeyer, J.; Yersin, H. Deep blue emitting Cu(I) tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence. Dalton Trans. 2018, 47, 17067–17076. doi: 10.1039/C8DT04093A
16. [16]
  Kubas, G. J. Inorg. Synth. 1990, 26, 68.
17. [17]
  Sheldrick, G. M. SHELXS-97, Program for Crystal Structure Solution. University of Göttigen, Germany 1997.
18. [18]
  Sheldrick, G. M. SHELXL-97, Program for Crystal Structure Refinement. University of Göttigen, Germany 1997.
19. [19]
  Kang, L.; Chen, J.; Teng, T.; Chen, X. L.; Yu, R.; Lu, C. Z. Experimental and theoretical studies of highly emissive dinuclear Cu(I) halide complexes with delayed fluorescence. Dalton Trans. 2015, 44, 11649–11659. doi: 10.1039/C5DT01292A
20. [20]
  Huang, C. H.; Wen, M.; Wang, C. Y.; Lu, Y. F.; Huang, X. H.; Li, H. H.; Wu, S. T.; Zhuang, N. F.; Hu, X. L. A series of pure-blue-light emitting Cu(I) complexes with thermally activated delayed fluorescence: structural, photophysical, and computational studies. Dalton Trans. 2017, 46, 1413–1419. doi: 10.1039/C6DT03965K
21. [21]
  Linfoot, C. L.; Leitl, M. J.; Richardson, P.; Rausch, A. F.; Chepelin, O.; White, F. J.; Yersin, H.; Robertson, N. Thermally activated delayed fluorescence (TADF) and enhancing photoluminescence quantum yields of [CuI(diimine)(diphosphine)]⁺ complexes-photophysical, structural, and computational studies. Inorg. Chem. 2014, 53, 10854–10861. doi: 10.1021/ic500889s
22. [22]
  Nitsch, J.; Lacemon, F.; Lorbach, A.; Eichhorn, A.; Cisnetti, F.; Steffen, A. Cuprophilic interactions in highly luminescent dicopper(I)-NHC-picolyl complexes-fast phosphorescence or TADF? Chem. Commun. 2016, 52, 2932–2935. doi: 10.1039/C5CC09659F
23. [23]
  Czerwieniec, R.; Leitl, M. J.; Homeier, H. H. H.; Yersin, H. Cu(I) complexes-thermally activated delayed fluorescence. Photophysical approach and material design. Coord. Chem. Rev. 2016, 325, 2–28. doi: 10.1016/j.ccr.2016.06.016
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