具有双吸电子基团D-A型配体的Ag(I)发光配合物的合成与性能研究

doi:10.6023/A24020058

摘要/Abstract

热活化延迟荧光(TADF)材料因其在有机发光二极管(OLED)材料领域具有巨大的应用前景, 受到了学术界的广泛关注. Ag(I)配合物的最外层电子排布为d¹⁰构型, d轨道始终处于填满状态, 不存在金属中心(MC)态, 因此不会发生MC态导致的淬灭效应, 适合用来设计开发TADF材料. 本研究中, 设计合成了一个新的D-A型配体, 9-(4'-(4,6-二苯基- 1,3,5-三嗪-2-基)-4-(3-(吡啶-2-基)-1H-吡唑-1-基)-[1,1'-联苯]-2-基)-3,6-二甲氧基-9H-咔唑(L). 该配体以3,6-二甲氧基- 9H-咔唑作为电子给体, 并含有三嗪和吡啶吡唑两个缺电子基团组成的双吸电子基团电子受体. 利用L为含氮双齿配体和双[2-(二苯基膦基)苯基]-醚(POP)为含磷双齿配体, 合成了离子型的Ag(I)配合物Ag(L)(POP)(BF₄) (1). 对配体L和配合物1进行了核磁共振氢谱、碳谱、元素分析以及X射线单晶衍射分析等表征. 其中配合物1属于三斜晶系, 空间群为P-1, 晶胞参数为a=1.30213(4) nm, b=1.63383(4) nm, c=1.93108(5) nm, α=92.941(2)°, β=105.247(3)°, γ=98.591(2)°, V=3.90076(18) nm³. Ag^＋离子在配合物1中为四配位, 并呈现出扭曲的四面体配位结构. 室温下, 配合物1固体在紫外灯照射下会发出强烈的绿光, 光谱峰值为490 nm, 荧光寿命为23.0 ns, 延迟荧光寿命为503.9 μs, 光致发光量子效率(PLQY)为43.8%. 对配合物1的不同温度发射光谱和寿命衰减研究表明, 配合物1固体在室温下呈现出热激活延迟荧光(TADF)特性.

关键词: Ag(I)配合物, 晶体结构, 光致发光, 密度泛函理论计算, 热活化延迟荧光

Thermally activated delayed fluorescence (TADF) materials have attracted significant attention in the field of organic light-emitting diodes (OLEDs) due to their tremendous application potential. The outermost electronic configuration of the Ag(I) complex is d¹⁰ configuration, with d orbitals always being filled. There is no metal-centred (MC) state, therefore the quenching effect caused by the MC state does not occur. This renders it an appropriate choice for the design and development of TADF materials. In this study, we designed and synthesized a novel D-A ligand, 9-(4'-(4,6-diphenyl-1,3,5-triazin-2-yl)-4- (3-(pyridin-2-yl)-1H-pyrazole-1-yl)-[1,1'-biphenyl]-2-yl)-3,6-dimethoxy-9H-carbazole (L). The ligand employs 3,6-dimeth- oxy-9H-carbazole as the electron donor and comprises a bis-electron-donating group comprising triazine and pyridyl pyrazole as the electron acceptor. An ionic Ag(I) complex, Ag(L)(POP)(BF₄) (1), was synthesised utilising L as a nitrogen-containing bidentate ligand and bis[2-(diphenylphosphino)phenyl] ether (POP) as a phosphorus-containing bidentate ligand. The ligand L and complex 1 were characterised by ¹H and ¹³C nuclear magnetic resonance spectrometry, elemental analysis and X-ray single crystal diffraction analysis. The complex 1 belongs to the triclinic crystal system with space group P-1, with a=1.30213(4) nm, b=1.63383(4) nm, and c=1.93108(5) nm, α=92.941(2)°, β=105.247(3)°, γ=98.591(2)°, V=3.90076(18) nm³. The Ag⁺ion in complex 1 is tetrahedrally coordinated with a twisted tetrahedral coordination geometry. At room temperature, complex 1 in solid form emits strong green light under UV light, with a maximum at 490 nm. The fluorescence lifetime is 23.0 ns, the thermally activated delayed fluorescence (TADF) lifetime is 503.9 μs, and the photoluminescence quantum yield (PLQY) is 43.8%. The steady-state emission spectra and time-dependent photoluminescent spectra of complex 1 at different temperatures demonstrate that complex 1 exhibits TADF characteristics at room temperature.

Key words: Ag(I) complex, crystal structure, photoluminescence, density functional theory calculation, thermally activated delayed fluorescence

引用此文

赵雨晴, 梁栋, 贾吉慧, 余荣民, 卢灿忠. 具有双吸电子基团D-A型配体的Ag(I)发光配合物的合成与性能研究[J]. 化学学报, 2024, 82(5): 486-492.

Yuqing Zhao, Dong Liang, Jihui Jia, Rongmin Yu, Can-Zhong Lu. Synthesis and Characterization of an Emissive Ag(I) Complex with a D-A Type Ligand Containing Two Electron-withdrawing Groups[J]. Acta Chimica Sinica, 2024, 82(5): 486-492.

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图/表 6

图1. 配体L(左)和配合物1(右)的ORTEP图

Figure 1. ORTEP diagram of ligand L (left) and complex 1 (right)

Compound
Distance/nm	Ag1—N1	0.2452(4)
	Ag1—N2	0.2295(4)
	Ag1—P1	0.24142(13)
	Ag1—P2	0.24334(12)
Angle/(°)	P1—Ag1—P2	116.69(4)
	P1—Ag1—N1	103.55(11)
	N1—Ag1—N2	69.85(15)
	N2—Ag1—P2	111.25(11)
Dihedral angle/(°)	P1—Ag1—P1/ N1—Ag1—N2	78.090(116)

表1. 配合物1的键长(nm)和键角(°)

Table 1. Bond lengths (nm) and bond angles (°) of complex 1

图2. (a)配体L和配合物1在CH2Cl2 (2×10?5 mol/L)溶液中的吸收光谱及其固体在298 K和77 K下的PL光谱(λEx=365 nm); (b)配合物1固体在298 K下的瞬态PL衰减光谱(λEx=365 nm, λEm=490 nm)

Figure 2. (a) Absorption spectra of complex 1 in CH2Cl2 (2×10?5 mol/L) solution and the PL spectra at 298 and 77 K in solid state (λEx=365 nm); (b) transient PL decay spectra at 298 K for complex 1 (λEx=365 nm, λEm=490 nm)

298 K
Compound	λ_max/ nm	Ф_PL/ %	Ф_F^a/ %	Ф_TADF^a/ %	τ_F/ ns	τ_TADF/ μs
L	490	17.3	17.0	0.3	106.0	3272.4
1	490	43.8	5.2	38.6	23.0	503.9

表2. 298 K下配体(L)和配合物1固态的光物理数据

Table 2. Photophysical data for ligand (L) and complex 1 in solid state at 298 K

图3. (a)配合物1在298 K下的时间分辨荧光光谱(λEx=365 nm, λEm=490 nm); (b)配合物1在77 K下的时间分辨荧光光谱(λEx=365 nm, λEm=530 nm)

Figure 3. (a) Time-resolved PL spectra of complex 1 in different time ranges at 298 K (λEx=365 nm, λEm=490 nm); (b) time-resolved PL spectra of complex 1 in different time ranges at 77 K (λEx=365 nm, λEm=530 nm)

图4. 配体L(左)和配合物1(右)的HOMO－1、HOMO、LUMO和LUMO＋1电子云分布

Figure 4. HOMO－1, HOMO, LUMO and LUMO＋1 electron cloud distribution of ligand L (left) and complex 1 (right)

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