Design, Synthesis and Properties of Cu(I) Complexes with a Nitrogen-containing Spirocycle Ligand for Delayed Fluorescence Materials

doi:10.6023/A24040148

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (8): 887-893.DOI: 10.6023/A24040148 Previous Articles Next Articles

Article

基于氮杂螺环配体的Cu(I)配合物延迟荧光材料的设计合成及性能研究

张登朝^a, 贾吉慧^a^,^*(), 梁栋^b^,^c, 蔡显宝^d, 赵雨晴^d, 胡祥龙^a, 江钰冰^a, 卢灿忠^b^,^c^,^*()

a 福建理工大学材料科学与工程学院福州 350118
b 中国科学院福建物质结构研究所福州 350108
c 中国科学院海西研究院厦门稀土材料研究中心厦门 361021
d 福州大学化学学院福州 350116

投稿日期:2024-04-30 发布日期:2024-06-12
基金资助:
国家自然科学基金(52073286); 国家自然科学基金(2021ZZ115); 国家自然科学基金(2021ZR132); 福建省自然科学基金(2021J011073); 福建省区域发展项目(2021H4008); 中国科学院科技服务网络计划(STS2023T3039)

Design, Synthesis and Properties of Cu(I) Complexes with a Nitrogen-containing Spirocycle Ligand for Delayed Fluorescence Materials

Dengchao Zhang^a, Jihui Jia^a^,^*(), Dong Liang^b^,^c, Xianbao Cai^d, Yuqing Zhao^d, Xianglong Hu^a, Yubing Jiang^a, Canzhong Lu^b^,^c^,^*()

a School of Materials Science and Engineering, FuJian University of Technology, Fuzhou 350118
b Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350108
c Xiamen Institute of Rare Earth Materials Haixi Institute, Chinese Academy of Sciences, Xiamen 361021
d College of Chemistry, Fuzhou University, Fuzhou 350116

Received:2024-04-30 Published:2024-06-12
Contact: * E-mail: jjhui@fjut.edu.cn; czlu@fjirsm.ac.cn
Supported by:
National Natural Science Foundation of China(52073286); National Natural Science Foundation of China(2021ZZ115); National Natural Science Foundation of China(2021ZR132); Natural Science Foundation of Fujian Province(2021J011073); regional development projects in Fujian Province(2021H4008); Science and Technology Service Network Initiative from the Chinese Academy of Sciences(STS2023T3039)

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Abstract

In this study, a Cu(I) complex luminescent material Cu-P-Spiro2N with thermally activated delayed fluorescence (TADF) properties was successfully designed by combining the donor-acceptor (D-A) type ligand 10-phenyl-10H-spiro[acridine-9,9'-(4,5-diazafluorene)] (Spiro2N) with long afterglow emission properties and the auxiliary phosphine ligand bis(2-diphenylphosphinophenyl) ether (POP). The molecular structures of the Cu(I) complex were confirmed by nuclear magnetic resonance spectroscopy, and the crystal structure of the Cu-P-Spiro2N complex was further characterized by X-ray single crystal diffraction. Cu-P-Spiro2N belongs to the triclinic crystal system with cell parameters α=90.14(2)°, β=115.43(3)°, γ=115.55(3)°, a=15.10(6) nm, b=15.15(4) nm, c=16.62(6) nm. Due to the two mutually orthogonal π-conjugated planar structures of the ligand molecule Spiro2N, its highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are well separated, but with a relatively large singlet-triplet energy gap (∆E_ST). After coordination of the metal Cu(I) fragment with the ligand Spiro2N, the energy gap between HOMO and LUMO is further reduced, and the charge transfer (CT) state energy level is further lowered, which makes the complex Cu-P-Spiro2N have a very small ∆E_ST of 0.05 eV. The small ∆E_ST facilitates the reverse intersystem crossing process, thereby achieving TADF emission. The emission of this complex mainly comes from the D-A ligand Spiro2N, which exhibits metal perturbation intramolecular ligand charge transfer (ILCT) properties. At room temperature, in the doped polymethylmethacrylate (PMMA) film (10% (w)), the Cu-P-Spiro2N complex exhibits strong yellow light emission with an emission peak at 551 nm, a photoluminescence quantum efficiency of 49%, and an excited state lifetime of 6.3 μs. The results of this study indicate that by coordinating with Cu(I) ions, the excited state energy level of the ligand molecule can be modulated, reducing ∆E_ST and thus achieving TADF emission.

Key words: Cu(I) complex, thermally activated delayed fluorescence, donor-acceptor type ligand, energy level tuning

Cite this article

Dengchao Zhang, Jihui Jia, Dong Liang, Xianbao Cai, Yuqing Zhao, Xianglong Hu, Yubing Jiang, Canzhong Lu. Design, Synthesis and Properties of Cu(I) Complexes with a Nitrogen-containing Spirocycle Ligand for Delayed Fluorescence Materials[J]. Acta Chimica Sinica, 2024, 82(8): 887-893.

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Fig. & Tab. 11

Figure 1. Crystal structure of complex Cu-P-Spiro2N

Figure 2. Thermogravimetric curve of complex Cu-P-Spiro2N

Figure 3. The HOMO and LUMO orbital distributions, frontier orbital energy levels, S1 and T1 energy levels of ligand Spiro2N and complex Cu-P-Spiro2N, as well as the electronic cloud distribution of ligand Spiro2N and complex Cu-P-Spiro2N in their S1 and T1 states under the S0 geometry configuration

Figure 4. The coordination geometry of complex Cu-P-Spiro2N in S0, S1, and T1 states optimized with DFT and TDDFT

Figure 5. The UV-visible absorption spectra of ligand Spiro2N and complex Cu-P-Spiro2N in CH2Cl2 solution (2×10?5 mol/L)

Figure 6. The photoluminescence spectra of complex Cu-P-Spiro2N in thin film state with 10% (w) PMMA doping concentration at 300 K and 77 K, as well as in the solid state at 300 K

Figure 7. Photoluminescence lifetime decay curve of complex Cu-P-Spiro2N in thin film state with 10% (w) PMMA doping concentration at 77 K

Figure 8. Steady-state spectrum and transient spectra at different delay times of complex Cu-P-Spiro2N in thin film state with 10% (w) PMMA doping concentration at 77 K

Figure 9. Photoluminescence spectrum of complex Cu-P-Spiro2N in CH2Cl2 solution (2×10?4 mol/L) at 300 K

Figure 10. Photoluminescence lifetime decay curve of complex Cu-P-Spiro2N in CH2Cl2 solution (2×10?4 mol/L) at 300 K after deoxygenation

Figure 11. Temperature-dependent lifetime curves and fitting parameters of complex Cu-P-Spiro2N

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基于氮杂螺环配体的Cu(I)配合物延迟荧光材料的设计合成及性能研究

Design, Synthesis and Properties of Cu(I) Complexes with a Nitrogen-containing Spirocycle Ligand for Delayed Fluorescence Materials

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