基于Zn（Ⅱ）-Ln（Ⅲ）的不对称希夫碱配合物的光致近红外发光及电致发光器件的研究
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摘要
稀土离子(4f)的近红外(NIR)特征发光近年来日一起了人们的广泛关注,主要是由于其在传感器、激光、光纤通讯、生物成像等方面具有显著的潜在应用价值。为了激发钕(Ⅲ)、铒(Ⅲ)、镱(Ⅲ)等镧系金属离子的近红外发光,克服镧系金属离子中宇称禁阻的f-f跃迁,人们设计了各种天线基团来敏化其特征发光。
本论文采用Zn(Ⅱ)的不对称希夫碱化合物作为发色团来敏化稀土离子的近红外发光,合成了24个新的Zn-Ln二核或多核化合物,并系统研究了其光致发光性质；并用筛选得到的化合物作为近红外发光二极管(OLED)的发光层主体材料,初步考察了其电致发光性能。
首先,用甲基-乙二胺与邻香草醛反应得到了不对称希夫碱(H2L1),以H2L1的Zn(Ⅱ)化合物[ZnL'Py](1)为前驱体,合成了Zn-Ln系列二核化合物[Zn(L1)Ln(N03)3Py](Ln=Nd,2；Ln=Yb,3；Ln=Er,4；Ln=Gd,5),确定了该系列化合物的的分子结构,并研究了其能量传递的规律；同时将重原子Br引入到H2L1得到H2L2,在此基础上合成了有重原子效应的Zn-Ln系列二核化合物[Zn(L2)Ln(N03)3Py](Ln=Nd,7；Ln=Yb,8；Ln=Er,9；Ln=Gd,10),并确定了其分子结构和光物理性质。
第二,用3-苯甲酰基-邻苯二胺与邻香草醛或溴代邻香草醛反应而得到两个不对称希夫碱H2L3和H2L4,分别以Zn(Ⅱ)配合物[ZnL3Py](11)和[ZnL4Py](16)为前驱体,合成得到Zn-Ln系列配合物(化合物Ln=Nd,12；Ln=Yb,13；Ln=Er, 14；Ln=Gd,15；化合物Ln=Nd,17；Ln=Yb,18；Ln=Er,19；Ln=Gd,20),利用光谱学的手段对H2L3和H2L4的Zn(II)-Ln(III)配合物结构进行分析,确定其结构并且研究了其他们的光物理性质。
第三,基于以上思考,用3-羟基-邻苯二胺而得到另外两个配体H3L5和H3L6,“一锅法”直接合成两者的锌-吡啶化合物[ZnHL5Py](21)和[ZnHL6Py](22),以此为前驱体合成他们的Zn-Ln配合物[Zn2(L5)Ln2(N03)4(Py)2(DMF)2](Ln=Nd, 23；Ln=Yb,24；Ln=Er,25；Ln=Gd,26)和[Zn2(L6)Ln2(N03)4(DMF)4](Ln=Nd, 27；Ln=Yb,28；Ln=Er,29；Ln=Gd,30),并确定了其分子结构、电子吸收光谱、电子发射光谱、量子产率及荧光寿命及天线基团对稀土离子的能量传递速率常数,并考察了重原子及吡啶对该体系化合物的红外发光性能的影响。
第四,从以上系列化合物中选取代表性的化合物[Zn(L2)Yb(NO3)3Py] (8)掺杂CuPc作为发光层的主体材料制作红外发光器件。器件结构为ITO/TPD(40 nm)/CuPc(x%, x= 0,5,10,15):8 (30 nm)/TPBI/LiF:Al (1:150 nm),电致发光位置在λem= 980 nm,表明这类化合物在近红外有机发光二极管中具有潜在的应用价值。
Near-infrared (NIR) luminescence of 4f rare earth ions has increasingly attracted great interest over the last few years, because of the potential significant technical applications in sensor, laser system, optical telecommunications and fluorescent imaging. Till now, a variety of antenna groups have been designed to sensitize the NIR luminescence from Nd(III), Er(III), Yb(III) ions, overcoming very low extinction coefficients resulting from parity-forbidden f-f transitions of lanthanide ions.
In this thesis, the NIR luminescence from the lanthanide(III) ions is sensitized from asymmetric Schiff base zinc compounds. Twenty four new compounds were synthesized, and their luminescent properties were also studied in detail. By selecting an obtained complex with preferable optical property as the host material, a NIR OLED was fabricated and its near-infrared electroluminescence was checked.
Firstly, the asymmetric schiff-base ligand (H2L1) was obtained from the reaction of methyl-ethylenediamine and o-vanillin in good yield. With the [ZnL1Py] as the precursor, the series of Zn-Ln bimetallic compounds [Zn(L1)Ln(NO3)3Py] (Ln= Nd, 2; Ln=Yb,3; Ln= Er,4; Ln= Gd,5) were assembled. Their molecular structures were characterized and the intra-molecular energy transfer was also studied. Furthermore, another series of Zn-Ln bimetallic compounds [Zn(L2)Ln(NO3)3Py] (Ln= Nd,7; Ln=Yb,8; Ln=Er,9; Ln= Gd,10) based on the replacement of H2L2 with the heavy-atom (Br) effect. Their molecular structures and photophysical properties were also discussed.
Secondly, two new asymmetric schiff-base ligands of H2L3 and H2L4 were obtained by the condensation reaction of 3-benzoyl-o-phenylenediamine with o-vanillin or 5-bromo-3-methoxy-benzaldehyde. Two series of bimetallic Zn-Ln compounds (complexes 12-15 and complexes 17-20) were obtained. Their structures were characterized by EA, FT-IR, UV-Visble absorption spectra, and the photophysical properties were discussed.
Two series of cyclic tetranuclear Zn2-Ln2 compounds (complexes 12-15 and complexes 17-20) were obtained. Their structures were characterized by EA, FT-IR, UV-Visble absorption spectra, and the photophysical properties were discussed.
Thirdly, two asymmetrical Schiff base ligands H2L5 and H2L6 were designed and in situ synthesized on the basis of above idea with the use of using 2,3-diaminophenol to obtain the two precursors [ZnHL5Py] (21) and [ZnHL6Py] (22). From the further self-assembly, two series of cyclic tetranuclear Zn2-Ln2 compounds [Zn2(L5)Ln2(NO3)4(Py)2(DMF)2] (Ln= Nd,23; Ln=Yb,24; Ln= Er,25; Ln= Gd, 26) and [Zn2(L6)Ln2(NO3)4(DMF)4] (Ln= Nd,27; Ln=Yb,28; Ln= Er,29; Ln= Gd, 30) were obtained.Their luminescent properties were examined, and the affect of heavy atom (Br) and the axial occupation of Py groups on the 3d Zn(II) ions was also analysized.
Finally, a NIR OLED device was fabricated by doping the selected complex 8 and CuPc as the host material of the emitting layer. The structure of device was ITO/TPD(40 nm)/CuPc(x%, x= 0,5,10,15):8 (30 nm)/TPBI/LiF:Al (1:150 nm). The solid NIR EL spectra showed that theλem lies at 980 nm, similar to that of solution, which validates the potential applications on NIR OLED.
本论文采用Zn(Ⅱ)的不对称希夫碱化合物作为发色团来敏化稀土离子的近红外发光,合成了24个新的Zn-Ln二核或多核化合物,并系统研究了其光致发光性质；并用筛选得到的化合物作为近红外发光二极管(OLED)的发光层主体材料,初步考察了其电致发光性能。
首先,用甲基-乙二胺与邻香草醛反应得到了不对称希夫碱(H2L1),以H2L1的Zn(Ⅱ)化合物[ZnL'Py](1)为前驱体,合成了Zn-Ln系列二核化合物[Zn(L1)Ln(N03)3Py](Ln=Nd,2；Ln=Yb,3；Ln=Er,4；Ln=Gd,5),确定了该系列化合物的的分子结构,并研究了其能量传递的规律；同时将重原子Br引入到H2L1得到H2L2,在此基础上合成了有重原子效应的Zn-Ln系列二核化合物[Zn(L2)Ln(N03)3Py](Ln=Nd,7；Ln=Yb,8；Ln=Er,9；Ln=Gd,10),并确定了其分子结构和光物理性质。
第二,用3-苯甲酰基-邻苯二胺与邻香草醛或溴代邻香草醛反应而得到两个不对称希夫碱H2L3和H2L4,分别以Zn(Ⅱ)配合物[ZnL3Py](11)和[ZnL4Py](16)为前驱体,合成得到Zn-Ln系列配合物(化合物Ln=Nd,12；Ln=Yb,13；Ln=Er, 14；Ln=Gd,15；化合物Ln=Nd,17；Ln=Yb,18；Ln=Er,19；Ln=Gd,20),利用光谱学的手段对H2L3和H2L4的Zn(II)-Ln(III)配合物结构进行分析,确定其结构并且研究了其他们的光物理性质。
第三,基于以上思考,用3-羟基-邻苯二胺而得到另外两个配体H3L5和H3L6,“一锅法”直接合成两者的锌-吡啶化合物[ZnHL5Py](21)和[ZnHL6Py](22),以此为前驱体合成他们的Zn-Ln配合物[Zn2(L5)Ln2(N03)4(Py)2(DMF)2](Ln=Nd, 23；Ln=Yb,24；Ln=Er,25；Ln=Gd,26)和[Zn2(L6)Ln2(N03)4(DMF)4](Ln=Nd, 27；Ln=Yb,28；Ln=Er,29；Ln=Gd,30),并确定了其分子结构、电子吸收光谱、电子发射光谱、量子产率及荧光寿命及天线基团对稀土离子的能量传递速率常数,并考察了重原子及吡啶对该体系化合物的红外发光性能的影响。
第四,从以上系列化合物中选取代表性的化合物[Zn(L2)Yb(NO3)3Py] (8)掺杂CuPc作为发光层的主体材料制作红外发光器件。器件结构为ITO/TPD(40 nm)/CuPc(x%, x= 0,5,10,15):8 (30 nm)/TPBI/LiF:Al (1:150 nm),电致发光位置在λem= 980 nm,表明这类化合物在近红外有机发光二极管中具有潜在的应用价值。
Near-infrared (NIR) luminescence of 4f rare earth ions has increasingly attracted great interest over the last few years, because of the potential significant technical applications in sensor, laser system, optical telecommunications and fluorescent imaging. Till now, a variety of antenna groups have been designed to sensitize the NIR luminescence from Nd(III), Er(III), Yb(III) ions, overcoming very low extinction coefficients resulting from parity-forbidden f-f transitions of lanthanide ions.
In this thesis, the NIR luminescence from the lanthanide(III) ions is sensitized from asymmetric Schiff base zinc compounds. Twenty four new compounds were synthesized, and their luminescent properties were also studied in detail. By selecting an obtained complex with preferable optical property as the host material, a NIR OLED was fabricated and its near-infrared electroluminescence was checked.
Firstly, the asymmetric schiff-base ligand (H2L1) was obtained from the reaction of methyl-ethylenediamine and o-vanillin in good yield. With the [ZnL1Py] as the precursor, the series of Zn-Ln bimetallic compounds [Zn(L1)Ln(NO3)3Py] (Ln= Nd, 2; Ln=Yb,3; Ln= Er,4; Ln= Gd,5) were assembled. Their molecular structures were characterized and the intra-molecular energy transfer was also studied. Furthermore, another series of Zn-Ln bimetallic compounds [Zn(L2)Ln(NO3)3Py] (Ln= Nd,7; Ln=Yb,8; Ln=Er,9; Ln= Gd,10) based on the replacement of H2L2 with the heavy-atom (Br) effect. Their molecular structures and photophysical properties were also discussed.
Secondly, two new asymmetric schiff-base ligands of H2L3 and H2L4 were obtained by the condensation reaction of 3-benzoyl-o-phenylenediamine with o-vanillin or 5-bromo-3-methoxy-benzaldehyde. Two series of bimetallic Zn-Ln compounds (complexes 12-15 and complexes 17-20) were obtained. Their structures were characterized by EA, FT-IR, UV-Visble absorption spectra, and the photophysical properties were discussed.
Two series of cyclic tetranuclear Zn2-Ln2 compounds (complexes 12-15 and complexes 17-20) were obtained. Their structures were characterized by EA, FT-IR, UV-Visble absorption spectra, and the photophysical properties were discussed.
Thirdly, two asymmetrical Schiff base ligands H2L5 and H2L6 were designed and in situ synthesized on the basis of above idea with the use of using 2,3-diaminophenol to obtain the two precursors [ZnHL5Py] (21) and [ZnHL6Py] (22). From the further self-assembly, two series of cyclic tetranuclear Zn2-Ln2 compounds [Zn2(L5)Ln2(NO3)4(Py)2(DMF)2] (Ln= Nd,23; Ln=Yb,24; Ln= Er,25; Ln= Gd, 26) and [Zn2(L6)Ln2(NO3)4(DMF)4] (Ln= Nd,27; Ln=Yb,28; Ln= Er,29; Ln= Gd, 30) were obtained.Their luminescent properties were examined, and the affect of heavy atom (Br) and the axial occupation of Py groups on the 3d Zn(II) ions was also analysized.
Finally, a NIR OLED device was fabricated by doping the selected complex 8 and CuPc as the host material of the emitting layer. The structure of device was ITO/TPD(40 nm)/CuPc(x%, x= 0,5,10,15):8 (30 nm)/TPBI/LiF:Al (1:150 nm). The solid NIR EL spectra showed that theλem lies at 980 nm, similar to that of solution, which validates the potential applications on NIR OLED.
引文
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