Synthesis of Rare Earth Polymer Complex Luminescent Materials

Synthesis of Modern Luminescent Lanthanide Molecular Complex Luminescent Materials Li Jianyu 1School of Chemical Engineering, Beijing Technology and Business University, Beijing 137. It is difficult to obtain polymer complexes with high luminescence intensity by reacting polymers; to make rare earth ions and polymer ligands and small molecule ligands At the same time, the product with better fluorescence intensity can be obtained. However, the reaction is difficult to quantitatively control; polymer complexes with high fluorescence intensity can also be obtained by polymerization of small molecule rare earth complexes, but the steric hindrance of the polymerization reaction is large, and an improved method is proposed for method 3.

The rare earth complexes have been widely used in the field of luminescence and display, especially their functional properties. The prospects for the development of functional molecules prepared by doping them into polymer matrices are even more remarkable. 1. However, doped rare earths The polymer luminescent material has inherent disadvantages and limits its application range. This is due to the phase separation between the two disadvantageous structures of the rare earth complex and the polymer material. Influencing the dispersion of rare earth ligands in the matrix material is not good, resulting in the annihilation of fluorescence. As a result, the light fraction decreases and the fluorescence intensity decreases. In the case of fluorescence lifetime, the rare-earth ions and the polymer are chemically bound to the rare-earth element. The luminescent material emerges at the right time. It has both the good electroluminescent properties of the rare earth complexes and the diversification of molecular materials. The performance greatly broadens the luminescence leanness. Complexes Rare earth polymer complex luminescent materials have not only been applied in laser and other fields4, but also show potential research value in some fields. Another example is to illustrate that organic tunable luminescence has low-voltage direct current drive, high luminance of 1;1, and easy realization of large areas of color, etc., and it is predicted that it will soon replace inorganic electroluminescence and become an important section of the display. technology. It is currently a hot topic in the international community. As the luminescent material of the device, the rare-earth complex has a narrow half-width band and a high color purity. This is unmatched by conjugated organic small molecule dyes and other metal chelates. It seems to be a thin molecule. Complexes produce light-emitting layers, making film formation difficult, and device preparation complicated, and crystallization tends to occur during film formation and use, which shortens the device lifetime. The polymerization of rare-earth complexes is expected to overcome this defect.

The study of rare earth polymer complex luminescent materials began in the early 1980s, but the development process was slow. In recent years, with the development of high-tech, the demand for rare-earth functional materials has become more and more severe and the pace of research and development in this area is increasing. In this article, three synthesis methods for rare-earth polymer complex light-emitting materials are proposed. The polymer reaction of the radicals This series of methods produces several series of luminescent rare earth macromolecule complexes. The polymer used has 3 types of polymers containing 0 carboxyl or sulfonic acid groups, such as styrene acrylic acid methyl methacrylate. Methyl propionate, acid styrene maleic acid 3 and other copolymers partially carboxylated or sulphonated polystyrene decayed vinyl naphthalene acrylic acid!

Copolymers such as vinyl styrene acrylic, polystyrene containing ketyl aryl ketone 3 moieties substituted by carboxyaroyl carboxybenzoyl 3 carboxy 2naphthoyl and 1 carboxy 8 naphthoyl.

Another inch of Ge-polymer dilute compound fluorescence properties, called. In addition to the mass fraction of the step complex + up to 15,05 and the mass fraction of the milk complex 4 up to 8, the rest of the complexes are! The mass fraction of 3+ is 45, and the fluorescence intensity can still increase with the addition of 1 content. If this level is exceeded, the monthly decline will be a phenomenon of concentration quenching. This is because rare-earth ions have abundant 54 and 4 orbits, and the coordination number is high, and the coordination number of rare earth ions in the complex synthesized in this manner is not satisfied, and ion aggregation occurs. In addition, the higher the ion concentration, the more coordination structures mono- and poly-ion ions are clustered into the clusters. The ions are relatively concentrated and the distance between the ions is reduced, and their interactions are strengthened, causing fluorescence quenching. Wang Hongwei et al12 prepared lanthanide complexes with a molar fraction of 13.5 and a degree of neutralization of 100 with a butyl acrylate acrylic copolymer polymer. When the mole fraction of 3+ is 34, the fluorescence intensity should be 3 when the mole fraction is 45. The maximal value, in turn, can quickly obtain a luminescent material with a higher fluorescence intensity.

2 Rare earth oysters simultaneously interact with macromolecule ligands and small molecule ligands In order to solve the problem that the above rare earth ion coordination numbers cannot be satisfied and high fluorescence intensity complexes cannot be prepared, the rare earth ions and macromolecular ligands are adopted. At the same time, the small molecule ligands JIA 8 and X 13 are introduced to the polymer containing the following styrene Chains and the small molecule ligands such as 8 hydroxy porphyrins. The phenanthroline and thiophene formyl fluoride acetone were synthesized with a 10-membered complex. The fluorescence intensity of these complexes was significantly higher than that of the corresponding rare-earth polymer complexes, in which the fluorescent intensity ratio of the +81 to 81-membered complexes. 16 yuan compound increased by 610 times.

Recently, it has been reported that the number of polymers falling on polymer chains containing the following chains is reduced. Observe the apparent concentration quenching phenomenon.

For rare-earth complexes of type 2 polymers, the fluorescence intensity of the rare-earth complexes is much weaker than that of the corresponding small-molecule rare-earth complexes. The researchers believe that this type of polymer is due to the occurrence of rare-earth ions and ketone structures in polymer systems. The steric hindrance of the reaction is large. The coordination number of the formed complex is low, resulting in weak fluorescence. And if the ketone structure group is in the polymer straight chain, the situation is worse than the side chain.

The rare-earth complexes of polymer-like polymers have a fluorescence intensity that increases after the maximum mass fraction is increased, and the trend is due to the increase in steric hindrance. This is due to the large steric hindrance and the low degree of rotation of the bond. Also coordinated, respectively with the inclusion of a 1-membered complex, the complexes are now better fluorescence. Fluorescence spectroscopy data shows that in this kind of structure complexes humans are the best small molecule ligands and polymers containing phenyl hydrazines can make the complexes get stronger fluorescence. Because of the small molecule ligands, rare earth ions can coordinate The number of factories to meet. Dilute polymer luminescent materials synthesized by this method do not cause concentration quenching. Furthermore, if a ligand with a good match between the heavy state energy level and the lowest excited state energy level of rare earth ions, such as a rare earth ion, is used, an ideal light emitting effect can be obtained. However, it is not difficult to understand that the probability of molecular ligands interacting with rare earth ions during the reaction is smaller than that of small molecule ligands. Department of the Great and the Great. 1. Elemental complexes of dilute ionic ions of small decagonal horses; and the reaction is difficult to quantify, and the composition of the product is difficult to control in the expected proportion. Therefore, +1 will give the best light effect.

3 Polymerization with a small molecule of a rare earth complex monomer, etc. 5 In view of the fact that method 1 fails to prepare a rare earth polymer complex with high emission intensity, a method of synthesizing a small molecule rare earth complex monomer and then copolymerizing it with styrene was adopted. They synthesized a complex monomer of 4-ethylenylbenzoylmethanebenzoylmethane with hydrazine and a complex monomer of 24-vinylbenzoylbenzoic acid-2-benzoylbenzoic acid with 0, The fluorescence intensity of the obtained complexes was linear with the increase of antimony content, and the strong effect Sun Zhaoyong first synthesized a small molecule complex containing acrylic acid with 1 lamp, and then copolymerized with methyl methacrylate to prepare a rare earth polymer complex. Compared with the corresponding small molecule complexes, the fluorescence lifetime is greatly extended, and the fluorescence intensity is significantly enhanced.

Wang Lianhui et al. Occupied 3+,3+,+, and this ketone with a rare earth ion, Acetyl acetone benzoyl methane 1 synergistic ligand, 252 dipyridyl and acrylic acid, prepared a variety of formula 2 identified 2 Jiang, a rare-earth multi-component complex monomer with polymerization activity and high efficiency luminescence was copolymerized with methyl methacrylate to synthesize a series of luminescent rare earth polymer complexes. The author of the comonomer composition reaction solvent initiator type and the amount of polymerization time polymerization temperature and other factors for a deeper study of this method, as the monomer of the rare earth complex volume. Polymediary has a large middle steric hindrance. The reaction will be difficult. However, the fluorescence effect of the product is ideal for the analysis and comparison of the synthetic routes of documents 1015,16. 1 In order to prepare rare earth ligand monomers, two kinds of polymerizable chelating agents are interposed, among which 4-vinyl benzoyl-2-benzoyl, carboxylic acid, rare-earth complexes of these compounds have low labor intensity and no application. value. The other is vinyl benzoyl benzoyl methyl bromide, which is a structural modification product of the translational ketone chelating agent benzoyl methane 08. 0 is just a good ligand of 1 melon red fluorescent complex, but the structure is Whether the modified compound has a good match with the lowest excited state energy level and whether even the ligand formed by itself and the heart 1 can generate fluorescence emission. The research report did not explain. If the above requirements can be met, why do we use two as ligands in the ligand monomer structure and instead use 01, if not, then it only has a coordination figure in the monomer of the complex, which will inevitably affect the coordination. The fluorescence intensity of the substance. What's more, they have only one oxime polymerization chelating agent in their monomer structure. That is, only vinyl. Not conducive to polymediated reaction.

In the monomer structure, ready-made excellent ketone ligands are used to ensure the luminescent properties of the materials, while the coordination between acrylic acid and rare earths is also used skillfully to introduce a vinyl structure with polymerization activity.

By avoiding the synthesis of chelating agents, the method is much simpler and results in better fluorescence. However, this also brings two ketones and other ligands in the complexes to have larger volumes than acrylic acid. This steric effect is not conducive to the occurrence of polymerization reactions. Or the position of the ligand such as 1, the ligand not only produces the same effect in the electroluminescence process. And for electroluminescence, its role in improving carrier transport is crucial.

From the above analysis, you can see the mountains. Both routes have + footholds. The author believes that in order to improve the coordination number of rare earth ions in rare-earth polymer complexes, the use of acrylic acid as a ligand is avoided. However, also + can be ordered to adopt the method of Document 10, should try to improve the polymerization activity of the rare earth complex monomer, that is, increase the number of vinyl groups in the monomer structure, it is required to participate in the coordination as possible chelating agent. Moreover, in order to ensure the fluorescence intensity of the complex, the chelating energy level of this chelating agent must have a good match with the lowest excited state energy of rare earth ions. The author has already begun to design and synthesize a kind of chelating agent allyl 254 pentanone in this aspect. The synthesis of several complex steroids is very good. 4 Conclusion The method 1 cannot prepare fluorescence. Higher strength rare earth polymer complexes are undesirable. Methods 2 and 3 can produce more ideal luminescent materials, and each has its own advantages and disadvantages. The main disadvantage of method 2 is that the probability of reacting polymer ligands with rare earth ions in the reaction system is small, and the composition of polymer complexes is difficult to control quantitatively; method 3 can synthesize rare earth complex monomers according to the expected composition, but The volume is large and polymerization occurs, and the space is large. In contrast, Tier 3 can be slightly better than Tier 2 but still needs improvement.

From the perspective of the research on the synthesis of rare-earth molecules with six light-emitting materials, foreign work started earlier. In the early 1980s, there were more, more and more, and our research, spoon, and walk in the forefront of the world were particularly worthwhile. It is noted that there have recently been reports of the application of luminescent rare earth molecular complexes to electro-mechanical electroluminescence.19 In foreign literature, similar work has not yet been done. I believe with the photoluminescence. Special foot electroluminescence study + cut-depth.

The development of new rare earth polymer complex luminescent materials will soon become a hot topic in the world. Li Jianyu, Zhang Songpei, Zeng Hong. Current Status and Prospects of Research on Rare Earth Complexes Photoconversion Agents Jiang Tao, Zeng Fanpan. Poly-8, 5-Hydroxy-5,5-nitrobenzene quinoline metal chelate of 3 Yao Ruigang, Liao Hua, Wu Shuguang et al. Study on the Fluorescence Spectra and Fluorescence Lifetime of Polymer Composite Films Containing Rare Earths. The 7th National Conference on Molecular Spectroscopy. Beijing Peking University Press, 1992.27272 6 Sun Gang, Zhao Yu, Yu Wei et al. Membrane 3+ organic complex as the emitting layer of organic thin film electrical 7 Zheng Ze, Zeng Fandi, Xiong Haijuan. Polymerization of 8 - hydroxyquinoline and its application prospects 12 WANG Hong - yu, LI Zhi - an, SONG Gui - zhen and so on. Effects of Different Synthetic Methods on Fluorescence Properties of Rare Earth Ionomers Polymer Materials Science and Engineering, 19941032730 15 Sun Zhaoyong, Wang Xinfeng, Chen Jianxin et al. Study on Luminescent Properties of é“• 1 Thiophene Acylfluorofluoroacetone Acrylic Acid Complexes and Their Polymers . Luminescence Journal, 1998, 19 16 Wang Lianhui, Ling Qidan, Zhang Wengong et al. Methyl methacrylate and rare earth complex monomer 17 Li Wenlian. Development of Rare Earth Organic Electroluminescence. Chinese Journal of Rare Earths, 1999, 17 18 Li Jianyu, Yu Qun, Zeng Hong et al. Synthesis of 3 allyl 2 4 pentanone and its photoluminescent properties of rare earth complexes. Chemical Bulletin, 7:16. ie 19 Zhao Dongxu, Li Wenlian, Hong Ziruo et al. Photo-induced ionic polymer macromolecular complexes 2, Zhao Dongxu, Li Wenbian, Hong Ziruo et al.é“• Polymer complexes Red thin film electroluminescence. On page 7, the level of technological innovation in the pesticide industry in China is private. The development of key technologies for research and industrialization of new pesticides will significantly improve the technological innovation capability and market competitiveness of the pesticide industry.

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