CN103436255A - Preparation method of lanthanide ion loaded metal-organic framework material capable of realizing lighting adjustability and sensing property - Google Patents
Preparation method of lanthanide ion loaded metal-organic framework material capable of realizing lighting adjustability and sensing property Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 20
- 229910021644 lanthanide ion Inorganic materials 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 14
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 13
- 229910020366 ClO 4 Inorganic materials 0.000 claims abstract description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 24
- 238000002791 soaking Methods 0.000 abstract description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
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- 238000010586 diagram Methods 0.000 description 7
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- 150000002500 ions Chemical class 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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Abstract
一种负载镧系离子实现发光可调和传感的金属-有机框架材料的制备方法，是以Zn(NO3)2·6H2O、(NH4)6Mo7O24·4H2O和均苯四甲酸二酐为原料，经过配位得到的一个配合物，将配合物浸泡在EuCl3或Tb(ClO4)3的溶液中，分别得到镧系掺杂配合物，再将上述掺杂配合物浸泡在MClx溶液中，分别得到配合物M–Eu[NH4]2[ZnL]·6H2O、M–Tb[NH4]2[ZnL]·6H2O。本发明是通过简单的浸泡得到一种新型具有发光可调和传感的镧系MOFs分子，这种镧系掺杂操作方便、稳定、高效、重复性强、对MOFs的发光可调和传感性能有很好的调控作用。
A method for preparing a metal - organic framework material loaded with lanthanide ions to realize tunable luminescence and sensing . pyromellitic dianhydride as raw material, a complex obtained through coordination, the complex is soaked in the solution of EuCl 3 or Tb(ClO 4 ) 3 to obtain the lanthanide doping complex respectively, and then the above doping complex The compounds were soaked in MCl x solution to obtain complexes M–Eu[NH 4 ] 2 [ZnL]·6H 2 O and M–Tb[NH 4 ] 2 [ZnL]·6H 2 O, respectively. The present invention obtains a novel lanthanide MOFs molecule with adjustable luminescence and sensing through simple soaking. Very good regulation.
Description
技术领域 technical field
本发明属于无机化学领域，特别涉及一种负载镧系离子实现发光可调和传感的金属-有机框架材料的制备方法。 The invention belongs to the field of inorganic chemistry, and in particular relates to a preparation method of a metal-organic framework material loaded with lanthanide ions to realize adjustable luminescence and sensing.
背景技术 Background technique
由于发光金属-有机框架材料（MOFs）拥有大的比表面积、孔径大且分布均匀、合成简单、结构可以预测等优点，注定了其在生物医学、环境、分子传感、发光器件等方面具有潜在的应用价值。MOFs 材料具有有机配体和无机金属离子两种成分，并且其结构特性，相比于有机发光材料和无机发光材料来说，比较复杂。因此 MOFs 材料发光现象可以有多种起源，如：基于有机配体发光、基于镧系离子发光、基于客体分子发光、基于电荷转移引起的发光。 Due to the advantages of large specific surface area, large pore size and uniform distribution, simple synthesis, and predictable structure, luminescent metal-organic framework materials (MOFs) are destined to have potential in biomedicine, environment, molecular sensing, and light-emitting devices. application value. MOFs materials have two components, organic ligands and inorganic metal ions, and their structural characteristics are more complicated than organic light-emitting materials and inorganic light-emitting materials. Therefore, the luminescence phenomenon of MOFs materials can have multiple origins, such as: luminescence based on organic ligands, luminescence based on lanthanide ions, luminescence based on guest molecules, and luminescence based on charge transfer.
基于镧系离子的发光是 MOFs 材料最常见的发光形式之一。镧系离子的电子跃迁因其受 5d 外壳保护，很少受其周围化学环境的影响，因而形成的MOFs 材料发出的光色纯度好，基本是镧系离子窄的特征发射峰。特别是 Eu3+和Tb3+ Luminescence based on lanthanide ions is one of the most common forms of luminescence in MOFs. Because the electronic transition of lanthanide ions is protected by the 5d shell, it is rarely affected by the surrounding chemical environment. Therefore, the formed MOFs materials emit light with good color purity, which is basically a narrow characteristic emission peak of lanthanide ions. Especially Eu 3+ and Tb 3+
的发射光具有寿命长、强度强、光成线性等优点，而受到广泛研究。但是，由于镧系离子中 4f 轨道跃迁是不可能发生的，从而对光的吸收比较弱，产生低效率的电子激发，发出的光的强度非常弱。因此单独使用镧系离子发光是不现实的。在 MOFs 材料中，由于有机配体与镧系离子的配位作用的存在，恰好解决了这个难题。其发光机理能用天线效应解释，大致可以分为三步：有机配体吸收能量；能量从配体转移到镧系离子上；镧系离子产生光。有机配体的敏化效应直接影响到发光材料的好坏，因此在制备镧系发光 MOFs 时必须小心选择合适的有机配体。在考虑合适的有机配体时，必须遵循的条件是：有机配体的最低三重态能级高于或者等于镧系离子的共振能，这样才能使有机配体的电荷转移到镧系离子上去，形成镧系发光 MOFs。 The emitted light has the advantages of long life, strong intensity, and light linearity, and has been widely studied. However, since the 4f orbital transition in lanthanide ions is impossible, the absorption of light is relatively weak, resulting in low-efficiency electron excitation, and the intensity of emitted light is very weak. Therefore, it is unrealistic to use lanthanide ions alone to emit light. In MOFs materials, due to the existence of coordination between organic ligands and lanthanide ions, this problem has just been solved. The luminescence mechanism can be explained by the antenna effect, which can be roughly divided into three steps: organic ligands absorb energy; energy is transferred from ligands to lanthanide ions; lanthanide ions generate light. The sensitization effect of organic ligands directly affects the quality of light-emitting materials, so the appropriate organic ligands must be carefully selected when preparing lanthanide light-emitting MOFs. When considering a suitable organic ligand, the condition that must be followed is that the lowest triplet energy level of the organic ligand is higher than or equal to the resonance energy of the lanthanide ion, so that the charge of the organic ligand can be transferred to the lanthanide ion, Formation of lanthanide light-emitting MOFs.
虽然镧系离子的发光机制（金属-配体间的配位作用或超分子定向能力）为设计和制备镧系发光MOFs提供了思路，然而根据当前晶体工程学的研究状况来看，合理地设计和制备镧系发光MOFs仍未能很好的实现，国内外有关镧系MOFs的发光传感研究还处在不成熟阶段。目前，最大的难题就是探索出一种高效的、重复性强的制备方法来实现MOFs的发光可调和传感。 Although the luminescent mechanism of lanthanide ions (coordination between metals and ligands or supramolecular orientation ability) provides ideas for the design and preparation of lanthanide luminescent MOFs, according to the current research status of crystal engineering, it is reasonable to design And the preparation of lanthanide luminescent MOFs has not yet been well realized, and the research on luminescence sensing of lanthanide MOFs at home and abroad is still in an immature stage. At present, the biggest challenge is to explore an efficient and reproducible preparation method to realize the luminescence tunability and sensing of MOFs.
发明内容 Contents of the invention
本发明的目的就是提供一种操作方便、稳定、高效、重复性强的负载镧系离子实现发光可调和传感的金属-有机框架材料的制备方法。 The purpose of the present invention is to provide a method for preparing a metal-organic framework material that is easy to operate, stable, efficient, and highly repeatable to load lanthanide ions to realize adjustable luminescence and sensing.
本发明的负载镧系离子实现发光可调和传感的金属-有机框架材料的制备方法，是以Zn(NO3)2·6H2O、(NH4)6Mo7O24·4H2O和均苯四甲酸二酐为原料，经过配位得到的一个配合物[NH4]2[ZnL]·6H2O ,其中L为均苯四甲酸，其一维的菱形孔道被抗衡离子NH4 +所占据，将此配合物浸泡在EuCl3或Tb(ClO4)3的溶液中，可分别得到镧系离子掺杂配合物Eu[NH4]2[ZnL]·6H2O和Tb[NH4]2[ZnL]·6H2O。然后将Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O浸泡在MClx溶液中，（M = Na+或K+或Zn2+或Ni2+或Mn2+或Co2+或Cu2+，当M为Na+或K+时，X为1；当M为Zn2+或Ni2+或Mn2+或Co2+或Cu2+时，X为2），分别得到配合物M–Eu[NH4]2[ZnL]·6H2O和M–Tb[NH4]2[ZnL]·6H2O，其具体制备方法是： The preparation method of the metal-organic framework material that supports lanthanide ions to realize adjustable luminescence and sensing of the present invention is based on Zn(NO 3 ) 2 ·6H 2 O, (NH 4 ) 6 Mo 7 O 24 ·4H 2 O and Pyromellitic dianhydride as raw material, a complex [NH 4 ] 2 [ZnL]·6H 2 O obtained through coordination, in which L is pyromellitic acid, and its one-dimensional rhombic channel is counter ion NH 4 + Occupied by soaking this complex in EuCl 3 or Tb(ClO 4 ) 3 solution, the lanthanide ion-doped complex Eu [NH 4 ] 2 [ZnL]·6H 2 O and Tb [NH 4 ] 2 [ZnL]·6H 2 O. Then Eu [NH 4 ] 2 [ZnL]·6H 2 O, Tb [NH 4 ] 2 [ZnL]·6H 2 O were soaked in MCl x solution, (M = Na + or K + or Zn 2+ or Ni 2+ or Mn 2+ or Co 2+ or Cu 2+ , when M is Na + or K + , X is 1; when M is Zn 2+ or Ni 2+ or Mn 2+ or Co 2+ or Cu 2 + when X is 2), the complexes M–Eu [NH 4 ] 2 [ZnL]·6H 2 O and M–Tb [NH 4 ] 2 [ZnL]·6H 2 O are obtained respectively, and the specific preparation methods are:
（1）取1mmol Zn(NO3)2·6H2O，1mmol (NH4)6Mo7O24·4H2O和0.5mmol 均苯四甲酸二酐放入聚四氟乙烯反应釜中，加10ml水作溶剂，放置在马弗炉中，加热到200℃，恒温144小时，然后以每小时3摄氏度降到室温或自然风干，得到无色块状晶体配合物[NH4]2[ZnL]·6H2O，L=均苯四甲酸。 (1) Take 1mmol Zn(NO 3 ) 2 6H 2 O, 1mmol (NH 4 ) 6 Mo 7 O 24 4H 2 O and 0.5mmol pyromellitic dianhydride in a polytetrafluoroethylene reactor, add 10ml of water was used as a solvent, placed in a muffle furnace, heated to 200°C, kept at a constant temperature for 144 hours, and then cooled to room temperature at 3°C per hour or dried naturally to obtain a colorless massive crystal complex [NH 4 ] 2 [ZnL] · 6H 2 O, L = pyromellitic acid.
（2）将配合物[NH4]2[ZnL]·6H2O 浸泡在10-3–10-6mol/L EuCl3或10-3–10-7mol/L Tb(ClO4)3的溶液中，分别得到镧系离子掺杂配合物Eu[NH4]2[ZnL]·6H2O和Tb[NH4]2[ZnL]·6H2O。 (2) Soak the complex [NH 4 ] 2 [ZnL]·6H 2 O in 10 -3 -10 -6 mol/L EuCl 3 or 10 -3 -10 -7 mol/L Tb(ClO 4 ) 3 In the solution, the lanthanide ion-doped complexes Eu [NH 4 ] 2 [ZnL]·6H 2 O and Tb [NH 4 ] 2 [ZnL]·6H 2 O were obtained respectively.
（3）取上述配合物Eu[NH4]2[ZnL]·6H2O或Tb[NH4]2[ZnL]·6H2O浸泡在10-2mol/L MClx溶液中，分别得到金属离子浸入的镧系掺杂配合物M–Eu[NH4]2[ZnL]·6H2O或M–Tb[NH4]2[ZnL]·6H2O，M= Na+或K+或Zn2+或Ni2+或Mn2+或Co2+或Cu2+。 (3) Soak the above complex Eu [NH 4 ] 2 [ZnL]·6H 2 O or Tb [NH 4 ] 2 [ZnL]·6H 2 O in a 10 -2 mol/L MCl x solution to obtain metal Ion-immersed lanthanide-doped complex M–Eu [NH 4 ] 2 [ZnL]·6H 2 O or M–Tb [NH 4 ] 2 [ZnL]·6H 2 O, M=Na + or K + or Zn 2+ or Ni 2+ or Mn 2+ or Co 2+ or Cu 2+ .
本发明的负载镧系离子实现发光可调和传感的金属-有机框架材料的制备方法，是通构过简单的浸泡得到一种新型具有发光可调和传感的镧系MOFs分子，这种镧系离子掺杂操作方便、稳定、高效、重复性强、对MOFs的发光可调和传感性能有很好的调控作用。 The preparation method of the metal-organic framework material that supports lanthanide ions to realize adjustable luminescence and sensing of the present invention is to obtain a new type of lanthanide MOFs molecule with adjustable luminescence and sensing through simple soaking. This lanthanide The ion doping operation is convenient, stable, efficient, and highly repeatable, and it has a good control effect on the luminescence and sensing performance of MOFs.
附图说明 Description of drawings
图1为本发明的配合物[NH4]2[ZnL]·6H2O沿c轴方向的三维结构图及其一维的菱形孔道； Fig. 1 is a three-dimensional structural diagram of the complex [NH 4 ] 2 [ZnL]·6H 2 O along the c-axis direction of the present invention and its one-dimensional diamond-shaped channel;
图2为本发明的配合物[NH4]2[ZnL]·6H2O浸泡在不同浓度EuCl3水溶液中的荧光光谱图； Fig. 2 is the fluorescence spectrum diagram of the complex [NH 4 ] 2 [ZnL]·6H 2 O soaked in different concentrations of EuCl 3 aqueous solution of the present invention;
图3为本发明的配合物[NH4]2[ZnL]·6H2O浸泡在不同浓度Tb(ClO4)3水溶液中的荧光光谱图； Fig. 3 is a fluorescence spectrum diagram of the complex [NH 4 ] 2 [ZnL]·6H 2 O soaked in different concentrations of Tb(ClO 4 ) 3 aqueous solutions of the present invention;
图4为本发明的配合物Eu[NH4]2[ZnL]·6H2O浸泡在10-2mol/L MClx(M = Na+,K+,Zn2+,Ni2+,Mn2+,Co2+,Cu2+)水溶液中分别在5D0-7F2或5D4-7F5的跃迁强度图； Figure 4 shows the complex Eu [NH 4 ] 2 [ZnL]·6H 2 O soaked in 10 -2 mol/L MCl x (M = Na + , K + , Zn 2+ , Ni 2+ , Mn 2 + , Co 2+ , Cu 2+ ) transition strength diagrams at 5 D 0 - 7 F 2 or 5 D 4 - 7 F 5 in aqueous solution;
图5为本发明的配合物Tb[NH4]2[ZnL]·6H2O浸泡在10-2mol/L MClx(M = Na+,K+,Zn2+,Ni2+,Mn2+,Co2+,Cu2+)水溶液中分别在5D0-7F2或5D4-7F5的跃迁强度图； Figure 5 shows the complex Tb [NH 4 ] 2 [ZnL]·6H 2 O soaked in 10 -2 mol/L MCl x (M = Na + , K + , Zn 2+ , Ni 2+ , Mn 2 + , Co 2+ , Cu 2+ ) transition strength diagrams at 5 D 0 - 7 F 2 or 5 D 4 - 7 F 5 in aqueous solution;
图6为本发明的配合物Eu[NH4]2[ZnL]·6H2O浸泡在不同浓度CuCl2或CoCl2水溶液中的荧光光谱图； Fig. 6 is a fluorescence spectrum diagram of the complex Eu [NH 4 ] 2 [ZnL]·6H 2 O soaked in different concentrations of CuCl 2 or CoCl 2 aqueous solutions of the present invention;
图7为本发明的配合物Tb[NH4]2[ZnL]·6H2O浸泡在不同浓度CuCl2或CoCl2水溶液中的荧光光谱图。 Fig. 7 is a fluorescence spectrum diagram of the complex Tb [NH 4 ] 2 [ZnL]·6H 2 O soaked in different concentrations of CuCl 2 or CoCl 2 aqueous solutions of the present invention.
具体实施方式 Detailed ways
实施例1： Example 1:
取1mmolZn(NO3)2·6H2O，1mmol(NH4)6Mo7O24·4H2O和0.5mmol均苯四甲酸二酐放入聚四氟乙烯反应釜中，加10mL水作溶剂，放置在马弗炉中，加热到200℃，恒温144小时，自然风干可得到无色块状晶体配合物[NH4]2[ZnL]·6H2O，其中L为均苯四甲酸；将配合物[NH4]2[ZnL]·6H2O 浸泡在10-3–10-6mol/L EuCl3或10-3–10-7mol/L Tb(ClO4)3的溶液中，可分别得到镧系掺杂的配合物Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O；将配合物Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O浸泡在10-2mol/L MClx（(M = Na+,K+,Zn2+,Ni2+,Mn2+,Co2+,Cu2+)溶液中，又可分别得到金属离子浸入的镧系掺杂配合物M–Eu[NH4]2[ZnL]·6H2O、M–Tb[NH4]2[ZnL]·6H2O。 Take 1mmol Zn(NO 3 ) 2 6H 2 O, 1mmol (NH 4 ) 6 Mo 7 O 24 4H 2 O and 0.5mmol pyromellitic dianhydride into a polytetrafluoroethylene reactor, add 10mL water as solvent , placed in a muffle furnace, heated to 200°C, kept at a constant temperature for 144 hours, and naturally air-dried to obtain a colorless blocky crystal complex [NH 4 ] 2 [ZnL]·6H 2 O, where L is pyromellitic acid; Complex [NH 4 ] 2 [ZnL]·6H 2 O soaked in 10 -3 -10 -6 mol/L EuCl 3 or 10 -3 -10 -7 mol/L Tb(ClO 4 ) 3 solution, can The lanthanide-doped complexes Eu [NH 4 ] 2 [ZnL]·6H 2 O and Tb [NH 4 ] 2 [ZnL]·6H 2 O were respectively obtained; the complex Eu [NH 4 ] 2 [ZnL]· 6H 2 O, Tb [NH 4 ] 2 [ZnL]·6H 2 O soaked in 10 -2 mol/L MCl x ((M = Na + ,K + ,Zn 2+ ,Ni 2+ ,Mn 2+ ,Co 2+ , Cu 2+ ) solution, the lanthanide-doped complex M–Eu [NH 4 ] 2 [ZnL]·6H 2 O, M–Tb [NH 4 ] 2 [ZnL] can be obtained respectively ]·6H 2 O.
分别对这几种配合物进行EA、ICP、PXRD分析，由PXRD分析可发现Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O与[NH4]2[ZnL]·6H2O的晶格不同，而M–Eu[NH4]2[ZnL]·6H2O、M–Tb[NH4]2[ZnL]·6H2O （M = Co2+,Cu2+）的晶格也分别与Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O不相同；通过ICP分析可知，由配合物[NH4]2[ZnL]·6H2O到Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O，发生了Eu(Ⅲ)或 Tb(Ⅲ)与(NH4)+的阳离子交换，而Eu[NH4]2[ZnL]·6H2O、Tb[NH4]2[ZnL]·6H2O到M–Eu[NH4]2[ZnL]·6H2O、M–Tb[NH4]2[ZnL]·6H2O，Co2+或Cu2+取代了 Eu(Ⅲ)/Tb(Ⅲ)和(NH4)+。发光性、传感性能研究表明：（1）配合物在[NH4]2[ZnL]·6H2O 在波长为437nm处具有强荧光性，呈蓝光发射，这可能是配体到金属的电荷转移所致。（2）配合物[NH4]2[ZnL]·6H2O浸泡在10-3 mol/L EuCl3所得的Eu[NH4]2[ZnL]·6H2O发光为红光发射；当EuCl3的溶液浓度在10-6 mol/L以下时，镧系离子掺杂的配合物对发光可调的作用微乎其微。（3）配合物[NH4]2[ZnL]·6H2O浸泡在10-3 mol/L Tb(ClO4)3所得的Tb[NH4]2[ZnL]·6H2O为绿光发射；当Tb(ClO4)3的溶液浓度在10-7 mol/L以下时，镧系离子掺杂的配合物对发光可调的作用微不足道。这两种镧系离子掺杂的配合物的发射光谱呈现出Eu(Ⅲ)或 Tb(Ⅲ)离子的特征发射光谱。（4）金属离子浸入的镧系掺杂配合物M–Eu[NH4]2[ZnL]·6H2O、M–Tb[NH4]2[ZnL]·6H2O的发光性主要取决于金属离子特性：Na+,K+,Zn2+对配合物的发光强度没有影响，而其他几种金属离子则对配合物的发光强度具有猝灭效应。特别是，在M–Eu[NH4]2[ZnL]·6H2O中，Cu2+具有最明显的影响，而在M–Tb[NH4]2[ZnL]·6H2O中，Co2+具有最显著的影响。镧系离子掺杂的配合物Eu[NH4]2[ZnL]·6H2O或Tb[NH4]2[ZnL]·6H2O可作为高选择性、高灵敏度、低检测限的发光传感器来检测水溶液中的Cu2+或Co2+。 EA, ICP, and PXRD analysis were carried out on these complexes respectively. From the PXRD analysis, it can be found that Eu [NH 4 ] 2 [ZnL]·6H 2 O, Tb [NH 4 ] 2 [ZnL]·6H 2 O and [NH 4 4 ] 2 [ZnL]·6H 2 O has a different lattice, while M–Eu [NH 4 ] 2 [ZnL]·6H 2 O, M–Tb [NH 4 ] 2 [ZnL]·6H 2 O (M = Co 2+ , Cu 2+ ) are also different from Eu [NH 4 ] 2 [ZnL]·6H 2 O and Tb [NH 4 ] 2 [ZnL]·6H 2 O; Complex [NH 4 ] 2 [ZnL]·6H 2 O to Eu [NH 4 ] 2 [ZnL]·6H 2 O, Tb [NH 4 ] 2 [ZnL]·6H 2 O, Eu(Ⅲ) or Cation exchange of Tb(Ⅲ) with (NH 4 ) + , while Eu [NH 4 ] 2 [ZnL]·6H 2 O, Tb [NH 4 ] 2 [ZnL]·6H 2 O to M–Eu [NH 4 ] 2 [ZnL]·6H 2 O, M–Tb [NH 4 ] 2 [ZnL]·6H 2 O, Co 2+ or Cu 2+ replaced Eu(Ⅲ)/Tb(Ⅲ) and (NH 4 ) + . The study of luminescence and sensing performance shows: (1) The complex has strong fluorescence at the wavelength of 437nm in [NH 4 ] 2 [ZnL]·6H 2 O, and emits blue light, which may be the charge from the ligand to the metal. caused by transfer. (2) Eu [NH 4 ] 2 [ZnL]·6H 2 O obtained by soaking the complex [NH 4 ] 2 [ZnL]·6H 2 O in 10 -3 mol/L EuCl 3 emits red light; when EuCl When the solution concentration of 3 is below 10 -6 mol/L, the lanthanide ion-doped complex has little effect on the luminescence adjustment. (3) Tb [ NH 4 ] 2 [ZnL]·6H 2 O obtained by soaking complex [NH 4 ] 2 [ZnL]·6H 2 O in 10 -3 mol/L Tb(ClO 4 ) 3 emits green light ; When the solution concentration of Tb(ClO 4 ) 3 is below 10 -7 mol/L, the effect of lanthanide ion-doped complexes on luminescence adjustment is insignificant. The emission spectra of these two lanthanide ion-doped complexes exhibit the characteristic emission spectra of Eu(Ⅲ) or Tb(Ⅲ) ions. (4) The luminescence of the lanthanide-doped complex M–Eu [NH 4 ] 2 [ZnL]·6H 2 O and M–Tb [NH 4 ] 2 [ZnL]·6H 2 O mainly depends on Metal ion characteristics: Na + , K + , Zn 2+ have no effect on the luminescence intensity of the complex, while other metal ions have quenching effects on the luminescence intensity of the complex. In particular, in M–Eu [NH 4 ] 2 [ZnL]·6H 2 O, Cu 2+ has the most pronounced effect, while in M–Tb [NH 4 ] 2 [ZnL]·6H 2 O, Co 2+ has the most significant impact. Lanthanide ion-doped complex Eu [NH 4 ] 2 [ZnL]·6H 2 O or Tb [NH 4 ] 2 [ZnL]·6H 2 O can be used as a luminescent sensor with high selectivity, high sensitivity and low detection limit To detect Cu 2+ or Co 2+ in aqueous solution.
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