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

doi:10.6023/A24040148

化学学报 ›› 2024, Vol. 82 ›› Issue (8): 887-893.DOI: 10.6023/A24040148 上一篇下一篇

研究论文

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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摘要/Abstract

本研究通过采用具有室温磷光发射性质的给体-受体(D-A)型配体10-苯基-10H-螺[吖啶-9,9'-(4,5-二氮芴)](Spiro2N), 与辅助膦配体双(2-二苯基磷苯基)醚(POP)结合, 成功设计了具有热活化延迟荧光(TADF)性质的Cu(I)配合物发光材料Cu-P-Spiro2N. 通过核磁共振谱图确认了Cu(I)配合物的分子结构. 进一步利用X射线单晶衍射表征了配合物Cu-P-Spiro2N的晶体结构. 结果表明, 配合物Cu-P-Spiro2N属于三斜晶系, 晶胞参数分别为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. 由于配体分子Spiro2N具有两个相互正交的π共轭平面结构, 使得其最高占据分子轨道(HOMO)和最低未占分子轨道(LUMO)具有很小的重叠, 但具有相对较大的单重态-三重态能隙差(∆E_ST). 金属Cu(I)片段与配体Spiro2N配位后, 降低了HOMO-LUMO之间的能隙差, 电荷转移(CT)态能级下降. 这使得配合物Cu-P-Spiro2N具有极小的∆E_ST (0.05 eV). 小的∆E_ST有利于加速反系间窜越过程, 进而实现TADF发射. 该类配合物的发射主要来自于D-A型配体Spiro2N, 表现为金属微扰的配体内电荷转移(ILCT)性质. 室温下, 在掺杂的聚甲基丙烯酸甲酯(PMMA)薄膜(10% (w))中, 配合物Cu-P-Spiro2N表现出强烈的黄光发射, 发射峰值位于551 nm, 光致发光量子效率为49%, 激发态寿命为6.3 μs. 本研究结果表明, 通过Cu(I)离子配位, 可调控配体分子激发态能级, 降低∆E_ST, 从而实现TADF发射.

关键词: Cu(I)配合物, 热活化延迟荧光, D-A型配体, 能级调控

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

引用此文

张登朝, 贾吉慧, 梁栋, 蔡显宝, 赵雨晴, 胡祥龙, 江钰冰, 卢灿忠. 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[J]. 化学学报, 2024, 82(8): 887-893.

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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图/表 11

图1. 配合物Cu-P-Spiro2N的晶体结构

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

图2. 配合物Cu-P-Spiro2N的热重曲线

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

图3. 配体Spiro2N与配合物Cu-P-Spiro2N的HOMO和LUMO轨道分布、前线轨道能级、S1和T1能级以及在S0几何构型下的S1和T1态电子云分布图

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

图4. 配合物Cu-P-Spiro2N在优化的S0, S1和T1态下的配位几何构型

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

图5. 配体Spiro2N与配合物Cu-P-Spiro2N在CH2Cl2 (2×10?5 mol/L)溶液中的紫外?可见吸收光谱

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

图6. 配合物Cu-P-Spiro2N在10% (w) PMMA掺杂浓度的薄膜态下300 K和77 K时的光致发光光谱以及固态下300 K时的光致发光光谱

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

图7. 配合物Cu-P-Spiro2N在10% (w) PMMA掺杂浓度的薄膜态下77 K时的光致发光寿命衰减曲线

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

图8. 配合物Cu-P-Spiro2N在10% (w) PMMA掺杂浓度的薄膜态下77 K时的稳态光谱及不同延迟时间下的瞬态光谱

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

图9. 配合物Cu-P-Spiro2N在CH2Cl2溶液(2×10?4 mol/L)中300 K时的光致发光光谱

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

图10. 配合物Cu-P-Spiro2N在CH2Cl2溶液(2×10?4 mol/L)中300 K时除氧后的光致发光寿命衰减曲线

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

图11. 配合物Cu-P-Spiro2N的变温寿命曲线及拟合参数

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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