CN101302228A - Rare earth aromatic carboxylic acid organic complex and preparation thereof - Google Patents

Rare earth aromatic carboxylic acid organic complex and preparation thereof Download PDF

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CN101302228A
CN101302228A CNA2008101157086A CN200810115708A CN101302228A CN 101302228 A CN101302228 A CN 101302228A CN A2008101157086 A CNA2008101157086 A CN A2008101157086A CN 200810115708 A CN200810115708 A CN 200810115708A CN 101302228 A CN101302228 A CN 101302228A
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rare earth
dnba
phen
organic complex
aromatic carboxylic
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张敬畅
吕玉光
曹维良
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Beijing University of Chemical Technology
Hainan Institute of Science and Technology
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Beijing University of Chemical Technology
Hainan Institute of Science and Technology
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Abstract

The invention relates to rare earth aromatic carboxylic acid organic complexes. The structural general formula of the complexes is shown in formula (I), wherein RE is equal to Eu<3+> or Tb<3+>; 1 represents 1, 10-o-phenanthroline (1, 10-Phen); and 2 represents 3, 5-dinitrobenzoic acid (3, 5-DNBA). The chemical name of formula (I) is europium or terbium 3, 5-dinitrobenzoic acid-o-phenanthroline organic complexes, and the chemical formula of the organic complexes is RE (3, 5-DNBA)3 Phen; moreover, the rare earth organic complexes has excellent thermal stability. In addition, the invention also relates to a method for making the rare earth aromatic carboxylic acid organic complexes, and the technological line for making the organic complexes is simple and easy to carry out.

Description

A kind of rare earth aromatic carboxylic acid organic complex and preparation method thereof
Technical field
The present invention relates to the rare earth organic fluorescent materials technical field, be specifically related to rare earth aromatic carboxylic acid title complex and synthetic method thereof, this rare earth aromatic carboxylic acid title complex has photoluminescence and electroluminescent properties.
Background technology
Rare earth luminescent material can be divided into photoluminescence, cathodoluminescence, X ray is luminous and electroluminescent material etc., in fields such as laser, photoluminescence, electroluminescent title complexs bigger using value is arranged.
Organic carboxyl acid mainly refers to various aromatic carboxylic acids, wherein based on phenylformic acid and various derivative thereof, and because of the carboxylate ligand compound all has a lot of similarities, its synthetic and existing at home and abroad many reports of property research, its applied research is also increasing.Rare earth (Eu 3+, Tb 3+) the aromatic carboxylic acid solid complexes is that a class has higher stability and the higher luminescent material of luminous intensity [1], but photic not remarkable with electroluminescent intensity enhancing effect.Organic carboxyl acid is the aromatic carboxylic-acid compound especially, because its aromatic ring has bigger conjugation rigid plane, simultaneously also because they can be by Sauerstoffatom and the rare-earth ion coordination in the carboxyl, the rare earth aromatic carboxylic acid title complex that forms, having stability and luminescent properties preferably, is the rare earth organic fluorescent materials that a class has better application prospect.Discover, after introducing second part in the rare earth carboxylate ligand compound and forming ternary complex, can make they luminescent properties be improved significantly.
Document 1, Lin Qin, Fu Lianshe, Liang Yujun. synthetic and the photic and electroluminescent character [J] of novel rare-earth aromatic carboxylate complexe. Chinese rare-earth journal, 2003,21 (1): 19-23. has introduced rare earth (Eu 3+, Tb 3+) the aromatic carboxylic acid solid complexes, be that a class has higher stability and the higher luminescent material of luminous intensity, but photic and electroluminescent intensity enhancing DeGrain, synthetic rare earth organic complex solubility property is not good enough.
Document 2, Qian Guodong, Wang Minquan. rare earth (Eu 3+, Tb 3+) synthetic, the sign and the photoluminescent property [J] thereof of nitrogen heterocyclic ring title complex. luminous journal, 1998,19 (1): 60. documents 2 have been introduced rare earth (Eu 3+, Tb 3+) synthetic, the sign and the photoluminescent property thereof of nitrogen heterocyclic ring title complex, so far, the research work of this direction is still extensively being carried out, but the subject matter of the luminous Study on Complexes of this class rare earth aromatic carboxylic acid is, thermostability, sublimability, the solvability of rare earth aromatic carboxylic acid luminescent ligand compound self influenced the brightness of its photoluminescence, electroluminescent device, rare earth aromatic carboxylic acid luminescent ligand compound glow color is more single simultaneously, and range of application is narrower.
Summary of the invention
The purpose of this invention is to provide a kind of rare earth aromatic carboxylic acid organic complex, another object of the present invention provides the preparation method of this rare earth aromatic carboxylic acid organic complex.
Rare earth aromatic carboxylic acid organic complex provided by the invention, its general structure are seen formula (I):
Figure A20081011570800041
Formula (I)
Wherein, RE=Eu 3+Or Tb 3+, 1 represents 1, the 10-phenanthroline (1,10-Phen), 2 represent 3, and the 5-dinitrobenzoic acid (3,5-DNBA), the chemical name of formula (I) is: europium or terbium 3, and 5-2 nitrobenzoic acid-phenanthroline organic coordination compound, its chemical formula is: RE (3,5-DNBA) 3Phen, this rare earth organic complex has good thermostability.
Rare earth organic complex Eu (3,5-DNBA) 3Phen mixes up nano-TiO 2After, its electroluminescent intensity obviously strengthens, and this performance has enlarged the range of application of rare earth organic complex.
The concrete preparation process of rare earth aromatic carboxylic acid organic complex is:
A. getting volumetric molar concentration respectively is 0.1～0.2mol.L -1EuCl 3Or TbCl 3Ethanolic soln 10-20ml, under agitation adding volumetric molar concentration is 0.1～0.2mol.L -11, among the 10-Phen ethanolic soln 10-20ml, mix;
B. under 20 ℃～65 ℃ temperature, the mixing solutions with steps A slowly splashes into 3 while stirring, in the 5-DNBA ethanolic soln, and 3, the volumetric molar concentration of 5-DNBA ethanolic soln is 0.1～0.2mol L -1, volume is 20-30ml, EuCl in this reaction soln 3Or TbCl:3, the mol ratio of 5-DNBA:Phen is 1: 3～6: 1～3;
C. regulate above-mentioned reaction soln pH value to 6-7 with triethylamine, produce white precipitate, room temperature leaves standstill 12～24h, makes its slaking, and suction filtration is precipitated to no Cl with absolute ethanol washing -,, get the white solid rare earth organic complex 50～70 ℃ of oven dry.Its productive rate is more than 90%.
The rare earth organic complex Eu that embodiment 1 is obtained (3,5-DNBA) 3Phen carries out differential thermal-thermogravimetric analysis (TGA-DTA) under nitrogen protection, the results are shown in Figure 1, as seen from Figure 1 title complex Eu (3,5-DNBA) 3The endotherm(ic)peak of Phen about 245 ℃ do not followed weightless process, obviously is the crystal melting process of rare earth organic complex, and as seen the fusing point of this rare earth organic complex is 245 ℃.At 410 ℃ a strong endotherm(ic)peak is arranged, be accompanied by weightless approximately 75%, almost completely decompose.Illustrate Eu (3,5-DNBA) 3Phen title complex better heat stability.
The rare earth organic complex that embodiment 1,2 is obtained carries out examination of infrared spectrum, the results are shown in Figure 2, and its wave-number range is 400～4000cm -1
The rare earth organic complex sample that embodiment 3,4 is obtained carries out relatively (see figure 3) of fluorescence spectrum, as can be seen from the figure, Eu (3,5-DNBA) 3Phen and Tb (3,5-DNBA) 3Phen infrared spectrum and similar.From the ir data of rare earth compounding (1606,1530cm -1) can find out, 3,5-DNBA and rare earth ion have generated stable title complex.With 1, the 10-Phen part is compared, and behind the formation title complex, part is positioned at 3046cm -1Place's absorption peak disappears.In addition, ligand 1,10-Phen 2250cm -1The strong absorption peak of place's appearance-N=C stretching vibration, this absorption peak disappears after forming title complex, and 1, the stretching vibration of 10-Phen C=C key is at 1647cm -1Also there is the last one absorption peak at the place, and this absorption peak moves to 1560cm in title complex -1C-H out-of-plane deformation vibration (r C-H) by 740cm -1Move to 725cm -1Near, behind the formation title complex, absorption peak all moves to low frequency, illustrates 1, and two nitrogen-atoms are participated in coordinations among the 10-Phen.Compare with part, title complex is at 522cm -1Near strong absorption band has newly appearred in one, can think the stretching vibration absorption peak of O → RE coordinate bond, prove that the synthetic rare earth compounding is the structure of general formula (I).
As seen from Figure 3, when the fluorescent emission wavelength is fixed on 612nm, Eu (3,5-DNBA) 3The best excitation spectrum spike of Phen title complex is long to be 312nm.When the fluorescent emission wavelength is fixed on 545nm, and Tb (3,5-DNBA) 3The best excitation spectrum spike of Phen title complex is long to be 315nm.The characteristic fluorescence emission peak of europium complex is positioned at 612.0nm, is europium 5D 0- 7F 2Weak ruddiness is sent out in transition.The feature emission peak of terbium coordination compound is positioned at 545.0nm, belongs to terbium 5D 4- 7F 5Weak green glow is sent out in transition, illustrate Eu (3,5-DNBA) 3Phen and Tb (3,5-DNBA) 3The photoluminescence intensity of Phen title complex a little less than.
With the rare earth organic complex Eu among the embodiment 1 (3,5-DNBA) 3Phen mixes up nano-TiO 2After the fluorescence spectrum test result see Fig. 4.The characteristic fluorescence emission peak of europium complex is positioned at 595.8nm, the genus europium 5D 0- 7F 1Fluorescent orange is sent in transition, does not observe the electroluminescent of terbium coordination compound under identical conditions.In Device A { ITO/PVK:Eu (3,5-DNBA) 3Phen (60nm)/ZnS (80nm)/Al}, electroluminescent intensity is issued to 195cd/m at 11V 2, show rare earth organic complex Eu (3,5-DNBA) 3Phen mixes up nano-TiO 2Back electroluminescent intensity obviously strengthens.
Major advantage of the present invention is: and Eu (3,5-DNBA) 3Phen and Tb (3,5-DNBA) 3Phen belongs to the aromatic carboxylic-acid compound, because 3,5-dinitrobenzoic acid aromatic ring has bigger conjugation rigid plane, simultaneously also because they can be by Sauerstoffatom and the rare-earth ion coordination in the carboxyl, the rare earth aromatic carboxylic acid title complex that forms, having stability and luminescent properties preferably, is the rare earth organic fluorescent materials that a class has better application prospect.The used chemical synthesis operational path of the present invention is simple and easy to do, the product Heat stability is good that obtains.This rare earth organic complex mixes up nano-TiO 2Back electricity causes sends out fluorescence orange.
Description of drawings:
Fig. 1 is the differential thermal-thermogravimetric analysis figure of embodiment 1 gained sample, and wherein a is that differential thermal figure, b are thermal multigraph;
Fig. 2 is the infrared spectrogram of embodiment 1,2 gained samples, and wherein a is the spectrogram of embodiment 1, and b is the spectrogram of embodiment 2;
Fig. 3 is embodiment 3,4 gained samples and 3, the fluorescence spectrum comparison diagram of 5-DNBA, and wherein a is 3, the spectrogram of 5-DNBA, the Eu that b obtains for embodiment 3 (3,5-DNBA) 3The spectrogram of Phen, c be execute the Tb that example 4 obtains (3,5-DNBA) 3The spectrogram of Phen;
Fig. 4 is the electroluminescent spectrum figure of embodiment 1, and test voltage is 12V.
Embodiment
Embodiment 1
A press RE (3,5-DNBA) 3Phen expression theory measurement is got 0.1mol.L respectively -1EuCl 3Ethanolic soln 10ml under agitation adds 0.1mol.L -11,10-Phen ethanolic soln 10ml;
B. use 60 ℃ of heating in water bath then, under constantly stirring, slowly splash into 0.1mol.L -13,5-DNBA ethanolic soln 30ml;
C. transfer pH value to 6.5 with triethylamine, produce white precipitate.Room temperature leaves standstill above-mentioned reactant 24h, makes its slaking, and suction filtration is precipitated to no Cl with 95% washing with alcohol -, in 70 ℃ of baking ovens, dry, white solid rare earth organic complex Eu (3,5-DNBA) 3Phen.
Rare earth organic complex Eu (3,5-DNBA) 3Dopen Nano TiO among the Phen 2, improve the luminous intensity of rare earth organic complex.At first be the luminescent layer of fabricate devices, just with rare earth compounding Eu (3,5-DNBA) 3Phen, polymer PVK (polyvinyl carbazole) and nano-TiO 2Common molten in chloroform by 1: 3: 1 mass ratio.What adopt in the experiment is with 2mg chloroform dissolving 6mg polymer PVK and 2mg nano-TiO 2An ito glass sheet is put on the chassis of sol evenning machine and holds and uniform rotation, speed keeps 3000 rev/mins.Then chloroformic solution is dripped to the film that forms homogeneous transparent on the ito glass sheet of rotation.Subsequently 2 * 10 -3Al electrode on the evaporation under the vacuum tightness of Pa, the efficient lighting area of device is π * 2 2Mm 2Adopt the performance map 4 of the circuit assembly testing electroluminescent of single layer structure device, and in Device A { ITO/PVK:Eu (3,5-DNBA) 3Phen (60nm)/ZnS (80nm)/Al}, electroluminescent intensity is issued to 195cd/m at 11V 2
Embodiment 2
A press RE (3,5-DNBA) 3Phen expression theory measurement is got 0.2mol.L respectively -1TbCl 3Ethanolic soln 10ml under agitation adds 0.2mol.L -11,10-Phen ethanolic soln 10ml;
B. in 62 ℃ of water-baths, be heated to constant temperature, under constantly stirring, slowly splash into 0.2mol.L -1M-NBA ethanolic soln 30ml;
C. transfer pH value to 6.8 with triethylamine, produce white precipitate.Room temperature leaves standstill above-mentioned reactant 20h, makes its slaking, and suction filtration is precipitated to no Cl with 95% washing with alcohol -, in 65 ℃ of baking ovens, dry, white solid rare earth organic complex Tb (3,5-DNBA) 3Phen.
Embodiment 3
A press RE (3,5-DNBA) 3Phen expression theory measurement is got 0.25mol.L respectively -1EuCl 3Ethanolic soln 10ml under agitation adds 0.25mol.L -11,10-Phen ethanolic soln 10ml;
B. in 62 ℃ of water-baths, be heated to constant temperature, under constantly stirring, slowly splash into 0.25mol.L -1M-NBA ethanolic soln 30ml;
B transfers pH value to 7.0 with triethylamine, produces white precipitate, and room temperature leaves standstill above-mentioned reactant 23h, makes its slaking, and suction filtration is precipitated to no Cl with 95% washing with alcohol -, in 66 ℃ of baking ovens, dry, white solid rare earth organic complex Eu (3,5-DNBA) 3Phen.
Embodiment 4
A. press RE (3,5-DNBA) 3Phen expression theory measurement is got 0.3mol.L respectively -1TbCl 3Ethanolic soln 10ml under agitation adds 0.3mol.L -11,10-Phen ethanolic soln 10ml;
B. in 62 ℃ of water-baths, be heated to constant temperature, under constantly stirring, slowly splash into 0.3mol.L -1M-NBA ethanolic soln 30ml;
C. transfer pH value to 7.2 with triethylamine, produce white precipitate, room temperature leaves standstill above-mentioned reactant 22h, makes its slaking, and suction filtration is precipitated to no Cl with 95% washing with alcohol -, in 68 ℃ of baking ovens, dry, white solid rare earth organic complex Tb (3,5-DNBA) 3Phen.

Claims (2)

1. rare earth aromatic carboxylic acid organic complex, its general structure is suc as formula shown in (I):
Figure A2008101157080002C1
Formula (I)
Wherein, RE=Eu 3+Or Tb 3+, 1 represents 1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-(1,10-Phen), 2 represent 3, and the 5-dinitrobenzoic acid (3,5-DNBA); The chemical name of formula (I) is: europium or terbium 3, and the luxuriant and rich with fragrance sound of vomiting of 5-2 nitrobenzoic acid-neighbour quinoline organic coordination compound, its chemical formula is: RE (3,5-DNBA) 3Phen, this rare earth organic complex has good thermostability.
2. the preparation method of a rare earth aromatic carboxylic acid organic complex as claimed in claim 1, concrete preparation process is:
A. getting volumetric molar concentration respectively is 0.1～0.2mol.L -1EuCl 3Or TbCl 3Ethanolic soln 10-20ml, under agitation adding volumetric molar concentration is 0.1～0.2mol.L -11, among the 10-Phen ethanolic soln 10-20ml, mix;
B. under 20 ℃～65 ℃ temperature, the mixing solutions with steps A slowly splashes into 3 while stirring, in the 5-DNBA ethanolic soln, and 3, the volumetric molar concentration of 5-DNBA ethanolic soln is 0.1～0.2mol L -1, volume is 20-30ml, EuCl in this reaction soln 3Or TbCl: 3, the mol ratio of 5-DNBA: Phen is 1: 3～6: 1～3;
C. regulate above-mentioned reaction soln pH value to 6-7 with triethylamine, produce white precipitate, room temperature leaves standstill 12～24h, makes its slaking, and suction filtration is precipitated to no Cl with absolute ethanol washing -,, get the white solid rare earth organic complex 50～70 ℃ of oven dry.
CNA2008101157086A 2008-06-27 2008-06-27 Rare earth aromatic carboxylic acid organic complex and preparation thereof Pending CN101302228A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767998A (en) * 2010-01-26 2010-07-07 三峡大学 Method for lowering oxygen content of titanium carbide and titanium nitride powder
CN103059052A (en) * 2012-06-21 2013-04-24 中国人民银行印制科学技术研究所 Rare-earth metal compound and synthetic process thereof
CN104449672A (en) * 2014-11-21 2015-03-25 天津工业大学 Long-arm benzoic acid rare earth luminescent material and preparation method thereof
CN107603599A (en) * 2017-10-01 2018-01-19 桂林理工大学 A kind of Lanthanide complex blue emitting material and synthetic method
CN108640936A (en) * 2018-04-23 2018-10-12 西安石油大学 A kind of rare-earth luminescent material Eu (5-nsa)3(phen) complex and preparation method
CN113387967A (en) * 2021-03-31 2021-09-14 衡阳师范学院 Rare earth material based on diphenylamine-carbonyl benzoic acid and preparation method and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767998A (en) * 2010-01-26 2010-07-07 三峡大学 Method for lowering oxygen content of titanium carbide and titanium nitride powder
CN103059052A (en) * 2012-06-21 2013-04-24 中国人民银行印制科学技术研究所 Rare-earth metal compound and synthetic process thereof
CN103059052B (en) * 2012-06-21 2015-09-09 中国人民银行印制科学技术研究所 A kind of rare earth compound and synthesis technique thereof
CN104449672A (en) * 2014-11-21 2015-03-25 天津工业大学 Long-arm benzoic acid rare earth luminescent material and preparation method thereof
CN104449672B (en) * 2014-11-21 2017-05-24 天津工业大学 Long-arm benzoic acid rare earth luminescent material and preparation method thereof
CN107603599A (en) * 2017-10-01 2018-01-19 桂林理工大学 A kind of Lanthanide complex blue emitting material and synthetic method
CN108640936A (en) * 2018-04-23 2018-10-12 西安石油大学 A kind of rare-earth luminescent material Eu (5-nsa)3(phen) complex and preparation method
CN113387967A (en) * 2021-03-31 2021-09-14 衡阳师范学院 Rare earth material based on diphenylamine-carbonyl benzoic acid and preparation method and application thereof

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