CN1300280C - Metallic organic complex with tribo-luminescent performance and its preparation process - Google Patents
Metallic organic complex with tribo-luminescent performance and its preparation process Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910007926 ZrCl Inorganic materials 0.000 claims abstract description 7
- ZKTVYRYOUVWCIA-UHFFFAOYSA-N 9h-carbazole;sodium Chemical compound [Na].C1=CC=C2C3=CC=CC=C3NC2=C1 ZKTVYRYOUVWCIA-UHFFFAOYSA-N 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005390 triboluminescence Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000013110 organic ligand Chemical class 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- -1 (Dimethylphenylpyrazolone) terbium triiodide Chemical compound 0.000 description 1
- WRADANNQOTZBDC-UHFFFAOYSA-N 1-anthracen-9-ylethanol Chemical compound C1=CC=C2C(C(O)C)=C(C=CC=C3)C3=CC2=C1 WRADANNQOTZBDC-UHFFFAOYSA-N 0.000 description 1
- 241001469188 Duboisia Species 0.000 description 1
- QSACCXVHEVWNMX-UHFFFAOYSA-N N-acetylanthranilic acid Chemical compound CC(=O)NC1=CC=CC=C1C(O)=O QSACCXVHEVWNMX-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005166 mechanoluminescence Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
本发明公开了一种具有摩擦发光性能的金属有机配合物，其特征在于：其结构式为(C12H8N)2ZrCl2(THF)2，其中，THF为四氢呋喃。其制备方法为，在惰性气体气氛下，向四氢呋喃有机溶剂中分别加入咔唑钠盐和四氯化锆，搅拌使之溶解，反应至少16小时，再进行后处理，获得所需金属有机配合物。本发明的产物在通常条件下被撞击就可以目测到很强的绿光。The invention discloses a metal organic complex with triboluminescent properties, which is characterized in that the structural formula is (C 12 H 8 N) 2 ZrCl 2 (THF) 2 , wherein THF is tetrahydrofuran. The preparation method is as follows: under an inert gas atmosphere, add carbazole sodium salt and zirconium tetrachloride to the tetrahydrofuran organic solvent, stir to dissolve them, react for at least 16 hours, and then carry out post-treatment to obtain the desired metal-organic complex . When the product of the present invention is hit under normal conditions, strong green light can be visually observed.
Description
技术领域Technical field
本发明涉及一种含五元环的稠合杂环化合物的配合物，尤其是一种具有摩擦发光性能的含咔唑配体的金属有机配合物及其制备方法。The invention relates to a complex of condensed heterocyclic compounds containing five-membered rings, in particular to a metal-organic complex containing carbazole ligands with triboluminescent properties and a preparation method thereof.
背景技术 Background technique
通过将机械压力作用于某些固体而导致其发光的现象被称为摩擦发光(Triboluminescence，缩写为TL)，从广义上讲，也可称为机械发光，在此过程中，这类固体材料将机械能转变为光能。具有摩擦发光性能的材料可用于制造感压发光体、压力探测传感器及其它科学仪器的显示元件等。TL的历史较长，早在上个世纪，在G.E.Hardy，J.C.Baldwin，J.I.Zink，W.C.Kaska，P.-H.Liu，L.Duboisia，J.Am.Chem.Soc.1977，99，3552.中公开了几种含有芳香基团的物质具有摩擦发光性能，它们是菲，苊，邻苯二甲酸酸酐，(Ph3PO)2MnBr2，(Ph3PO)2MnCl2，[PhC(O)]3P＝P[C(O)Ph]3，Eu[CH(COC6H5)2]4，9-蒽基乙醇，乙酰氨茴酸。它们同时具有良好的荧光特性，但并不是所有具有良好荧光特性的材料都具有优良的摩擦发光性质，只有某些含有特定的配位体并具有特定的晶体结构的荧光物质才会有摩擦发光特性。一些人试图从晶体结构的角度以及摩擦激发空气来解释并揭示摩擦发光机理，但是至今科学界对此尚无定论。目前普遍认为，具有摩擦发光性能的化合物中结构为非中心对称的占90％以上。The phenomenon of luminescence caused by applying mechanical pressure to certain solids is called triboluminescence (abbreviated as TL). In a broad sense, it can also be called mechanoluminescence. In this process, such solid materials will Mechanical energy is converted into light energy. Materials with triboluminescent properties can be used to manufacture pressure-sensitive luminous bodies, pressure detection sensors, and display elements of other scientific instruments. TL has a long history, as early as the last century, in GE Hardy, JC Baldwin, JIZink, WCKaska, P.-H.Liu, L.Duboisia, J.Am.Chem.Soc.1977, 99, 3552. A substance containing aromatic groups has triboluminescent properties, they are phenanthrene, acenaphthylene, phthalic anhydride, (Ph 3 PO) 2 MnBr 2 , (Ph 3 PO) 2 MnCl 2 , [PhC(O)] 3 P =P[C(O)Ph] 3 , Eu[CH(COC 6 H 5 ) 2 ] 4 , 9-anthracenyl ethanol, acetylanthranilic acid. They have good fluorescent properties at the same time, but not all materials with good fluorescent properties have excellent triboluminescent properties, only certain fluorescent substances containing specific ligands and having specific crystal structures will have triboluminescent properties . Some people try to explain and reveal the mechanism of triboluminescence from the perspective of crystal structure and frictional excitation of air, but the scientific community has not yet reached a conclusion on this. At present, it is generally believed that among the compounds with triboluminescent properties, the non-centrosymmetric structure accounts for more than 90%.
文献报道，绝大多数具有摩擦发光性能的金属有机配合物的结构都是非中心对称的。在F.A.Cotton，L.M.Daniels，P.Huang，Inorganic Chemistry2001，40，3576.中公开了六种具有摩擦发光性能的金属配合物，(MePh3P)2MnCl4，(Et4N)2MnBr4，(Ph3PO)2MnBr2，(Ph3PO)2MnI2，(Ph3PO)2MnCl2和(Ph3AsO)2MnBr2，它们都为非中心对称结构。在F.A.Cotton，L.M.Daniels，P.Huang，Inorganic Chemistry Communications，2001，4，319.中公开了非中心对称结构的(NEt3H){Eu[CH(COC6H5)2]4}也具有摩擦发光的性能。在R.G.Xiong，X.Z.You，Inorganic Chemistry Communications，2002，5，677.中公开了配合物(C6H5CH2NH){Eu[CH(COC6H5)2]4}也有摩擦发光的性能，其结构也是非中心对称的。It has been reported in the literature that the structures of most metal-organic complexes with triboluminescent properties are non-centrosymmetric. In FA Cotton, LMDaniels, P. Huang, Inorganic Chemistry 2001, 40, 3576. six metal complexes with triboluminescent properties are disclosed, (MePh 3 P) 2 MnCl 4 , (Et 4 N) 2 MnBr 4 , (Ph 3 PO) 2 MnBr 2 , (Ph 3 PO) 2 MnI 2 , (Ph 3 PO) 2 MnCl 2 and (Ph 3 AsO) 2 MnBr 2 , all of which are noncentrosymmetric structures. Disclosed in FA Cotton, LMDaniels, P. Huang, Inorganic Chemistry Communications, 2001, 4, 319. (NEt 3 H){Eu[CH(COC 6 H 5 ) 2 ] 4 } with non-centrosymmetric structure also has triboluminescence performance. It is disclosed in RGXiong, XZYou, Inorganic Chemistry Communications, 2002, 5, 677. that the complex (C 6 H 5 CH 2 NH) {Eu[CH(COC 6 H 5 ) 2 ] 4 } also has triboluminescent properties, its The structure is also noncentrosymmetric.
具有摩擦发光性能的结构为中心对称的金属有机配合物也有报道。在A.L.Rheingold，W.King，Inorganic Chemistry，1989，28，1715.中公开了三种具有摩擦发光性能的金属有机配合物Eu[CH(COC6H5)(COCH3)]4(pip)，六(二甲基苯基吡唑酮)三碘化铽和[Tb(H2O)6Cl2]Cl，它们的结构都为中心对称的。在X.R.Zeng，R.G.Xiong，X.Z.You，K.K.Cheung，Inorganic ChemistryCommunications，2000，3，341.中公开了一种结构为中心对称的具有摩擦发光性能的金属有机配合物Eu[CH(COC6H5)2]4(mor)。Metal-organic complexes with triboluminescent properties have also been reported. In ALRheingold, W.King, Inorganic Chemistry, 1989, 28, 1715., three metal-organic complexes Eu[CH(COC 6 H 5 )(COCH 3 )] 4 (pip) with triboluminescent properties are disclosed, six (Dimethylphenylpyrazolone) terbium triiodide and [Tb(H 2 O) 6 Cl 2 ]Cl, both of which have centrosymmetric structures. In XRZeng, RGXiong, XZYou, KKCheung, Inorganic Chemistry Communications, 2000, 3, 341., a metal-organic complex Eu[CH(COC 6 H 5 ) 2 ] 4 ( mor).
因而，无法根据化合物的荧光特性或者结构是否对称来判断其有无摩擦发光性能。同时，到目前为止，还没有关于前过渡金属有机配合物具有摩擦发光性能的报道。由于具有摩擦发光性能的物质具备工业应用前景，人们在不断寻求新的具有摩擦发光性能的物质。Therefore, it is impossible to judge whether the compound has triboluminescent properties based on its fluorescence characteristics or whether its structure is symmetrical. Meanwhile, so far, there is no report on triboluminescent properties of early transition metal-organic complexes. Because the materials with triboluminescent properties have industrial application prospects, people are constantly looking for new materials with triboluminescent properties.
发明内容Contents of Invention
本发明目的是提供一种新的具有摩擦发光性能的金属有机配合物；The purpose of the present invention is to provide a new metal-organic complex with triboluminescent properties;
本发明的另一个目的是提供这种金属有机配合物的制备方法。Another object of the present invention is to provide a method for the preparation of this metal-organic complex.
为达到上述目的，本发明采用的技术方案是：一种具有摩擦发光性能的金属有机配合物，其结构式为(C12H8N)2ZrCl2(THF)2，其中，THF为四氢呋喃。In order to achieve the above purpose, the technical solution adopted in the present invention is: a metal-organic complex with triboluminescent properties, its structural formula is (C 12 H 8 N) 2 ZrCl 2 (THF) 2 , wherein THF is tetrahydrofuran.
为实现本发明的另一个发明目的，采用的技术方案是，一种具有摩擦发光性能的金属有机配合物的制备方法，在惰性气体气氛下，向四氢呋喃有机溶剂中分别加入咔唑钠盐(C12H8NNa)和四氯化锆(ZrCl4)，搅拌使之溶解，反应至少16小时，再进行后处理，获得所需金属有机配合物。In order to realize another object of the invention of the present invention, the technical scheme adopted is, a kind of preparation method of metal-organic complex with triboluminescence property, under inert gas atmosphere, add carbazole sodium salt (C 12 H 8 NNa) and zirconium tetrachloride (ZrCl 4 ), stirred to dissolve, reacted for at least 16 hours, and then post-treated to obtain the desired metal organic complex.
上述技术方案中，为使反应完全进行，所述加入的咔唑钠盐和四氯化锆的摩尔比为2∶1。In the above technical scheme, in order to make the reaction proceed completely, the molar ratio of the added carbazole sodium salt and zirconium tetrachloride is 2:1.
一般地，反应可以在室温下进行，但为了加快反应速度，也可以适当加热，进一步的技术方案为，所述反应温度在20-80℃之间。Generally, the reaction can be carried out at room temperature, but in order to speed up the reaction, it can also be properly heated. A further technical solution is that the reaction temperature is between 20-80°C.
上述技术方案中，所述后处理为，先通过离心去除析出的氯化钠，再对母液浓缩、冷冻，获得所需金属有机配合物。In the above technical solution, the post-treatment is to first remove the precipitated sodium chloride by centrifugation, and then concentrate and freeze the mother liquor to obtain the desired metal-organic complex.
本发明的制备过程中，采用的是金属卤化物、有机配体的盐和溶剂组成的体系，在惰性气氛下进行反应，反应温度通常为室温，其中，所述有机配体为含氮配体，所述溶剂为不含活泼氢的有机溶剂，反应体系必须除氧、除水，用惰性气体(如氩气或氮气)保护。In the preparation process of the present invention, a system composed of metal halides, organic ligand salts and solvents is used, and the reaction is carried out under an inert atmosphere. The reaction temperature is usually room temperature, wherein the organic ligand is a nitrogen-containing ligand , the solvent is an organic solvent that does not contain active hydrogen, and the reaction system must be deoxygenated and dehydrated, and protected with an inert gas (such as argon or nitrogen).
由于上述技术方案运用，本发明与现有技术相比具有下列优点：Due to the use of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art:
1.本发明制备过程中采用的金属卤化物为四氯化锆，锆是一种前过渡金属，以前过渡金属构成摩擦发光物质目前未见报道，因而本发明为寻求摩擦发光物质开辟了一条新路；1. The metal halide that adopts in the preparation process of the present invention is zirconium tetrachloride, and zirconium is a kind of former transition metal, and before transition metal constitutes triboluminescent material, there is no report at present, thus the present invention has opened up a new way for seeking triboluminescent material road;
2.本发明的产物在通常条件下被撞击就可以目测到很强的绿光。2. When the product of the present invention is hit under normal conditions, a strong green light can be visually observed.
具体实施方式 Detailed ways
下面结合实施例对本发明作进一步描述：The present invention will be further described below in conjunction with embodiment:
实施例一：Embodiment one:
带搅拌子的反应瓶经除氧、除水处理后，在氩气保护下加入0.2摩尔的咔唑钠盐C12H8NNa，0.1摩尔的ZrCl4，加入四氢呋喃作为溶剂，搅拌使反应物完全溶解，在室温下反应24小时。将反应体系进行离心处理，去除析出的固体氯化钠，再对母液浓缩、冷冻，即得到(C12H8N)2ZrCl2(THF)2，经测定，其为非中心对称结构[Crystal system：Orthorhombic；Space group：iba2]。在室温下撞击配合物(C12H8N)2ZrCl2(THF)2可以目测到很强的绿光。After the reaction bottle with stirring bar is deoxidized and dehydrated, under the protection of argon, add 0.2 mole of carbazole sodium salt C 12 H 8 NNa, 0.1 mole of ZrCl 4 , add tetrahydrofuran as a solvent, and stir to make the reactant completely Dissolved and reacted at room temperature for 24 hours. Centrifuge the reaction system to remove the precipitated solid sodium chloride, then concentrate and freeze the mother liquor to obtain (C 12 H 8 N) 2 ZrCl 2 (THF) 2 , which is non-centrosymmetric structure [Crystal system: Orthorhombic; Space group: iba2]. A strong green light can be visually detected by striking the complex (C 12 H 8 N) 2 ZrCl 2 (THF) 2 at room temperature.
Claims (4)
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| US6071632A (en) * | 1995-01-06 | 2000-06-06 | Ciba Specialty Chemicals Corporation | Triboluminescent lanthanideIII complexes |
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| US6071632A (en) * | 1995-01-06 | 2000-06-06 | Ciba Specialty Chemicals Corporation | Triboluminescent lanthanideIII complexes |
| CN1365381A (en) * | 2000-03-27 | 2002-08-21 | 出光兴产株式会社 | organic electroluminescent element |
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