CN1778786A - Rare-earth doped beta-diketone complex fluorescent powder its production and use - Google Patents
Rare-earth doped beta-diketone complex fluorescent powder its production and use Download PDFInfo
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Abstract
A rare-earth doped beta-diketo complex fluorescent powder, its production and use are disclosed. The formula equation is (RexLn1-X)AyB, R is rare-earth doped element from La, Y or Gd and 0<=X<=0.5; Ln is rare-earth luminescent central element from Eu, Tb Sm or Dy; A is beta-diketo ligand, B is o-phenanthroline and 2-2-dipyridine or 8-alkyl quinazine, when B is 8- alkyl quinazine, y=2; when B is o-phenanthroline and 2-2-dipyridine, y=3.
Description
Technical field
The present invention relates to a kind of rare-earth doped beta-diketone complex, it has high luminous efficiency and low cost, also relates to the manufacture method of this rare-earth doped beta-diketone complex and as the purposes of fluorescent material.
Background technology
(as Eu, Tb) the f-f transition can take place after being stimulated, present sharp-pointed wire bands of a spectrum, and excited state has the long relatively life-span, this is its luminous advantage to known rare earth ion.But rare earth ion is very little in the specific absorbance of near ultraviolet region, so luminous efficiency is lower.And high organic compound triplet excited state and the rare earth ion excited level of some specific absorbance is complementary, they as part and rare-earth ion coordination after, can give rare earth ion with its transmission ofenergy that absorbs in the near ultraviolet region effectively, make the luminous strength ratio of title complex cooperate preceding rare earth ion that remarkable increase is arranged.
Therefore, rare earth organic complex has the luminous intensity height, crest is narrow, bright-colored and good weatherability, light decay is little and be difficult for advantage such as oxidized and received concern.
Rare-earth doped beta-diketone complex is paid attention to by people as the research of hyperfluorescence title complex always, and this is that the title complex that beta-diketon and rare earth are generated is comparatively stable owing to exist chelate ring and comprise the movable conjugated link(age) of electronics in the title complex; And exist high efficiency energy transmission in this class title complex, thereby make that their luminous efficiencies in all rare earth organic complexes are the highest from beta-diketonate ligand to the rare earth central ion with high absorption coefficient.
Because rare-earth doped beta-diketone class title complex chemical property is stable and luminescent properties is excellent, therefore has broad application prospects.But because Eu, luminescence center ion costs such as Tb are higher, make this class title complex be subjected to certain restriction aspect industrialization.Therefore, need to seek a kind of beta-diketone complex of rare earth cheaply, it has low manufacturing cost and high luminous efficiency.
The synthetic general liquid phase synthesizing method that adopts of existing rare earth luminous title complex, it generally includes following steps:
1) the rare earth element muriate is dissolved in forms rare-earth chloride solution in the alcohol;
2) beta-diketonate ligand, o-phenanthroline and sodium hydroxide are dissolved in the alcohol, form ligand solution;
3) described rare-earth chloride solution is slowly added in the described ligand solution, the pH value of reaction mixture is adjusted to 6.5-7.0, reaction, ageing and remove unreacted organic ligand in hot water bath obtain product.
Though this method can make rear-earth-doped-beta-diketone complex needs a large amount of organic solvents, thereby operator and environment is polluted.
Therefore, need to seek a kind of solid phase synthesis process that need not rare-earth doped beta-diketone complex with an organic solvent.
The content of invention
The purpose of this invention is to provide a kind of rare-earth doped beta-diketone complex cheaply, it has low manufacturing cost and high luminous efficiency.
Another object of the present invention provides the method for the described rare-earth doped beta-diketone complex of a kind of solid phase synthesis, and it has and need not reaction solvent and the high advantage of reaction yield.
Therefore, the invention provides a kind of rare-earth doped beta-diketone class title complex with following general formula:
(Re
xLn
1-x)A
yB
In the formula, the Re representative is selected from La, the rear-earth-doped element of Y or Gd, 0≤x≤0.5;
The Ln representative is selected from Eu, Tb, the rare-earth luminescent center element of Sm or Dy;
The A representative has the beta-diketon class part of following general formula:
R wherein
1And R
2Can be identical or different, be selected from following group respectively
B represents o-phenanthroline, 2,2-dipyridyl or oxine;
When B is oxine, y=2;
When B is an o-phenanthroline, 2, during the 2-dipyridyl, y=3.
The present invention also provides a kind of manufacture method of described rare-earth doped beta-diketone class title complex, and it comprises the steps:
1. the acetate of lucium is provided;
2. when using o-phenanthroline or 2, during the 2-dipyridyl, press acetate, beta-diketon and the o-phenanthroline or 2 of 1: 3: 1 mixed in molar ratio lucium, the 2-dipyridyl; Perhaps when using oxine, by acetate, beta-diketon and the oxine of 1: 2: 1 mixed in molar ratio lucium;
With mixture heating up to 65-75 ℃, grind till product does not contain volatility acetic acid.
Description of drawings
Fig. 1 is the doping 30%La that makes with solid phase method in better example of the present invention
3+Eu (dbm)
3The infrared spectrogram of phen;
Fig. 2 is the doping 30%La that makes with existing liquid phase method
3+Eu (dbm)
3The infrared spectrogram of phen
Fig. 3 (a) mixes 50%La
3+The fluorescence spectrum figure of solid phase method synthetic europium-diphenylpropane-1,3-dione(DPPO)-o-phenanthroline title complex;
Fig. 3 (b) mixes 20%La
3+The fluorescence spectrum figure of solid phase method synthetic europium-diphenylpropane-1,3-dione(DPPO)-o-phenanthroline title complex;
Fig. 3 (c) is the fluorescence spectrum figure that does not mix the solid phase method synthetic europium-diphenylpropane-1,3-dione(DPPO)-o-phenanthroline title complex of other rare earth ion.
Embodiment
The inventor finds, La, and Y, Gd etc. have the fluorescence enhancement, and these rare earth elements that mix not only can improve the fluorescence intensity of luminescence rare earth beta-diketon class title complex, and can reduce cost.
Therefore, the invention provides a kind of general formula is (Re
xLn
1-x) A
yThe rare-earth doped beta-diketone class title complex of B.
In rare-earth doped beta-diketone class title complex of the present invention, Re is at least a La of being selected from, the rear-earth-doped element of Y or Gd.Compare with for example Eu, Tb, Sm or Dy as the rare-earth luminescent center element, the price of this class doped element is comparatively cheap.The content of this rear-earth-doped element can account for the 0-50 atom % of title complex middle-weight rare earths element total amount, is preferably 20-40 atom %, 25-35 atom % more preferably, the best 30 atom % that are generally.
Rare-earth doped beta-diketone class title complex of the present invention, if the triplet energy level of luminescence center ionic excited level and part coupling is better, and the ratio of dopant ion is appropriate, then the fluorescence property of title complex is better, can send strong fluorescence.In general, for a series of title complexs, when the doping of dopant ion is 30%, the fluorescence intensity of title complex is the strongest.
In rare-earth doped beta-diketone class title complex of the present invention, Ln represents a kind of Eu that is selected from, Tb, the rare-earth luminescent center element of Sm or Dy.Ln better is selected from Eu or Tb.
In rare-earth doped beta-diketone class title complex of the present invention, the A representative has the beta-diketon class part of following general formula:
R wherein
1And R
2Can be identical or different, be selected from following group respectively
The indefiniteness example of described beta-diketon class part has benzoyl acetone, diphenylpropane-1,3-dione(DPPO), benzoyltrifluoroacetone, naphthoyltrifluoroacetone or the like.
In rare-earth doped beta-diketone class title complex of the present invention, B represents o-phenanthroline, 2,2-dipyridyl or oxine;
When B is oxine, y=2;
When B is an o-phenanthroline, 2, during the 2-dipyridyl, y=3.
Rare-earth doped beta-diketone class title complex of the present invention can be used as fluorescent material.Compare with the fluorescent material of the non-fluorescent rare earth element that do not mix, the adulterated fluorescent material of the present invention is except the advantage of the good luminous performance, stable in properties and the long service life that keep non-doping fluorescent powder, and main also have an advantage of low manufacturing cost.
Fig. 3 (a) is the fluorescence spectrum of the Eu title complex of a better example of the present invention, its doping 50%La
3+, Fig. 3 (c) is the fluorescence spectrum of identical Eu title complex of La of not mixing.By Fig. 3 (a) and 3 (c) as seen, doping La
3+Do not influence luminous intensity.On the contrary, La
3+Further improved Eu
3+Luminous intensity.
The present invention also provides a kind of manufacture method of described rare-earth doped beta-diketone class title complex, and it comprises the steps:
The method that the present invention makes described rare-earth doped beta-diketone class title complex comprises the step that lucium acetate is provided.The method that forms lucium acetate is known in the art, for example can be referring to Witt J R.JInorg Nucl Chem, 1962,24:637.In a better example of the present invention, it comprises, by the rare earth atom number, with 0-50 atom %, be preferably 20-40 atom %, 25-35 atom % more preferably is preferably the La that is selected from of 30 atom %, the oxide compound of the rear-earth-doped element of Y or Gd and surplus be selected from Eu, Tb, the oxide compound of the rare-earth luminescent center element of Sm or Dy mixes mutually, adds the acetic acid of capacity, thereby makes described hopcalite change into the mixture of lanthanon acetate.
Make in the method for described rare-earth doped beta-diketone class title complex in the present invention, the acetate, the o-phenanthroline or 2 that are used for the mishmetal mixture, the 2-dipyridyl (perhaps oxine) and the method for beta-diketon are without particular limitation, and they can be the blending meanss of any routine.
Make in the method for described rare-earth doped beta-diketone class title complex in the present invention, the rare earth oxide and the beta-diketone compound of use all are commercially available.
The method that the present invention makes described rare-earth doped beta-diketone class title complex comprises mixture heating up grinds the step till product does not contain volatility acetic acid to 65-75 ℃.In the methods of the invention, the method that is used to heat is without particular limitation, and it can adopt the method for baking oven for heating, method of infrared lamp irradiated heat or the like.In a better example of the present invention, place 70 ℃ baking oven to heat in mixture, and take out to grind once, till being ground to no acetic acid and emitting, until react completely (about about 4 hours) every half an hour.
If necessary, can remove unnecessary reactant by washing, be about to solid product elder generation water and give a baby a bath on the third day after its birth time, wash with ethanol, vacuum-drying is then preserved.
Rare-earth doped beta-diketone class complex fluorescent powder of the present invention adopts solid-phase synthesis, utilize the sensibilized between the rare earth element, the choose reasonable part, thereby not only improved the luminous intensity of title complex, and reduced cost, reduced the pollution of building-up process to environment.
Fig. 1 is that infrared spectrogram, Fig. 2 of the fluorescence complex that makes with solid phase method of the present invention in better example of the present invention is the infrared spectrogram with Fig. 1 like products, but this product is to make with conventional liquid phase method.By Fig. 1 and Fig. 2 as seen, considerable change does not take place in both infrared spectras.Promptly can make the product identical with existing liquid phase method with solid phase method of the present invention.
Therefore, the present invention adopts the synthetic rare earth doped beta-diketon class of solid-phase synthesis title complex to have following advantage:
1) adopts solid-phase synthesis, do not need reaction solvent, reduce pollution, and method is simple, easily carries out scale operation environment;
2) product that makes mixes and has the non-fluorescent rare earth ion of fluorescence sensitivity effect, improves luminescent properties, reduces cost;
3) fluorescent material that makes with this title complex has characteristics such as good luminous performance, stable in properties, long service life.
Further specify the present invention below in conjunction with embodiment.
Embodiment
The testing method of luminous intensity
The plant and instrument of testing the fluorescence spectrum use of made title complex pressed powder is the Cary Eclipse of a U.S. VARIAN company type fluorophotometer.For adopting identical test condition with a series of title complexs.Relatively the luminous intensity with a series of complex fluorescent powders adopts the strongest emission peak in the fluorescence emission spectrum.Luminous intensity as table 1 is central ion Eu
3+Luminous intensity at the emission peak of 611nm.
Embodiment 1
Solid phase method synthesizes La
3+Doping Eu
3+-diphenylpropane-1,3-dione(DPPO)-o-phenanthroline ternary complex
Eu
3+With La
3+Mixing vinegar hydrochlorate, diphenylpropane-1,3-dione(DPPO) and o-phenanthroline feed intake at 1: 3: 1 by amount of substance.Luminescence rare earth ion Eu in the mixing vinegar hydrochlorate
3+With dopant ion La
3+Ratio as shown in table 1 below.
Take by weighing the o-phenanthroline of 0.002mol mixing vinegar hydrochlorate, 0.006mol diphenylpropane-1,3-dione(DPPO) and 0.002mol, reaction mixture is fully ground, mix, put into about 70 ℃ heating of baking oven, grind once per half an hour, and till no HAc emitted, reaction in about more than four hours was finished.Product is put into moisture eliminator and is preserved.
The fluorescence pattern of the sample that mensuration makes, its luminous intensity is listed in table 1.
Table 1
| Sample | Eu 3+∶La 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 205.8 |
| 2 | 0.5∶0.5 | 609.1 |
| 3 | 0.7∶0.3 | 662.9 |
| 4 | 0.8∶0.2 | 627.8 |
| 5 | 1.0∶0.0 | 590.9 |
By table 1 result as seen, when the content of doped with rare-earth elements was 90%, the luminous intensity of title complex descended to some extent.
Fig. 3 (a) is sample 2 fluorescence spectrums, and Fig. 3 (b) is the fluorescence spectrum of sample 4, and Fig. 3 (c) is the fluorescence spectrum of sample 5.Relatively as seen both fluorescence spectrums mix 50%La
3+The fluorescence intensity of europium-diphenylpropane-1,3-dione(DPPO) (a)-o-phenanthroline title complex is better than the fluorescence intensity of the europium-diphenylpropane-1,3-dione(DPPO)-o-phenanthroline title complex that does not mix other rare earth ion (c).
The infrared spectra of sample 3 can be referring to Fig. 1.
Comparative example 1
Liquid phase method synthesizes La
3+Doping Eu (III)-diphenylpropane-1,3-dione(DPPO)-o-phenanthroline ternary complex
Take by weighing 0.002mol Eu
3+With La
3+Mixed chloride be dissolved in 20mL 95% ethanol Eu
3+With La
3+Ratio be listed in the table below 2.Get the 0.002mol o-phenanthroline and be dissolved in the 20mL ethanol, and add the NaOH of 0.006mol diphenylpropane-1,3-dione(DPPO) and 0.006mol, place the water-bath about 50 ℃ to heat, stir simultaneously.The ethanolic soln that is dissolved with the 0.002mol rare earth chloride is slowly splashed in the ligand solution, and regulating the final pH value is 6.5～7.0, continues in hot water bath stirring reaction again 1 hour, ageing.Suction filtration with distilled water and 95% ethanol thorough washing, is removed unreacted organic ligand and Cl
-, vacuum-drying is preserved.
Table 2
| Sample | Eu 3+∶La 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 214.5 |
| 2 | 0.5∶0.5 | 570.4 |
| 3 | 0.7∶0.3 | 647.8 |
| 4 | 0.8∶0.2 | 610.4 |
| 5 | 1.0∶0.0 | 565.3 |
Fig. 2 is the infrared spectrogram of sample 3.
Comparison diagram 1 and Fig. 2 as seen, considerable change does not take place in the infrared spectra of the two, proves with solid phase method to make the product identical with liquid phase method.
Embodiment 2
With embodiment 1 described method synthetic compound, but be to use Sm
3+With La
3+Mixing vinegar hydrochlorate, diphenylpropane-1,3-dione(DPPO) and o-phenanthroline.The result is as shown in table 3.
Table 3
| Sample | Sm 3+∶La 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 215.2 |
| 2 | 0.5∶0.5 | 360.0 |
| 3 | 0.7∶0.3 | 401.5 |
| 4 | 0.8∶0.2 | 380.1 |
| 5 | 1.0∶0.0 | 353.9 |
Embodiment 3
With the method synthetic compound identical, but be to use Sm with embodiment 1
3+With La
3+Mixing vinegar hydrochlorate, benzoyltrifluoroacetone and o-phenanthroline, the results are shown in table 4:
Table 4
| Sample | Sm 3+∶La 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 300.1 |
| 2 | 0.5∶0.5 | 573.5 |
| 3 | 0.7∶0.3 | 613.6 |
| 4 | 0.8∶0.2 | 601.3 |
| 5 | 1.0∶0.0 | 577.8 |
Embodiment 4
With the method synthetic compound identical, but be to use Tb with embodiment 1
3+With Gd
3+Mixing vinegar hydrochlorate, benzoyltrifluoroacetone and o-phenanthroline.The results are shown in table 5.
Table 5
| Sample | Tb 3+∶Gd 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 98.1 |
| 2 | 0.5∶0.5 | 194.6 |
| 3 | 0.7∶0.3 | 224.3 |
| 4 | 0.8∶0.2 | 242.0 |
| 5 | 1.0∶0.0 | 225.9 |
Embodiment 5
With the method synthetic compound identical, but be to use Tb with embodiment 1
3+With Y
3+Mixing vinegar hydrochlorate, benzoyl acetone and oxine (1: 2: 1).The results are shown in following table 6.
Table 6
| Sample | Tb 3+∶Y 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 34.9 |
| 2 | 0.5∶0.5 | 70.3 |
| 3 | 0.7∶0.3 | 105.7 |
| 4 | 0.8∶0.2 | 102.8 |
| 5 | 1.0∶0.0 | 85.4 |
Embodiment 6
With the method synthetic compound identical, but be to use Dy with embodiment 1
3+With Y
3+Mixing vinegar hydrochlorate, benzoyltrifluoroacetone and 2, the 2-dipyridyl.In addition, after making product, wash this product with water three times, washing with alcohol successively once.The results are shown in table 7.
Table 7
| Sample | Dy 3+∶Y 3+Mol ratio | Luminous intensity |
| 1 | 0.1∶0.9 | 140.6 |
| 2 | 0.5∶0.5 | 260.2 |
| 3 | 0.7∶0.3 | 284.8 |
| 4 | 0.8∶0.2 | 272.1 |
| 5 | 1.0∶0.0 | 259.7 |
Claims (8)
1. rare-earth doped beta-diketone class title complex with following general formula:
(Re
xLn
1-x)A
yB
In the formula, the Re representative is selected from La, the rear-earth-doped element of Y or Gd, 0≤x≤0.5;
The Ln representative is selected from Eu, Tb, the rare-earth luminescent center element of Sm or Dy;
The A representative has the beta-diketon class part of following general formula:
R wherein
1And R
2Can be identical or different, be selected from following group respectively
B represents o-phenanthroline, 2,2-dipyridyl or oxine;
When B is oxine, y=2;
When B is an o-phenanthroline, 2, during the 2-dipyridyl, y=3.
2. rare-earth doped beta-diketone class title complex as claimed in claim 1 is characterized in that described beta-diketon class part is selected from benzoyl acetone, diphenylpropane-1,3-dione(DPPO), benzoyltrifluoroacetone, naphthoyltrifluoroacetone.
3. rare-earth doped beta-diketone class title complex as claimed in claim 1 or 2 is characterized in that 0.2≤x≤0.4.
4. rare-earth doped beta-diketone class title complex as claimed in claim 3 is characterized in that 0.25≤x≤0.35.
5. one kind as the manufacture method of rare-earth doped beta-diketone class title complex as described in each among the claim 1-4, and it comprises the steps:
1) provides the acetate of lucium;
2) when using o-phenanthroline or 2, during the 2-dipyridyl, press acetate, beta-diketon and the o-phenanthroline or 2 of 1: 3: 1 mixed in molar ratio lucium, the 2-dipyridyl; Perhaps when using oxine, by acetate, beta-diketon and the oxine of 1: 2: 1 mixed in molar ratio lucium;
3) with mixture heating up to 65-75 ℃, grind till product does not contain volatility acetic acid.
6. method as claimed in claim 5 is characterized in that it also comprises the product that obtains is washed removing the step of unnecessary reactant, and described washing step comprises successively uses washing with alcohol again with solid product washing three times.
7. as claim 5 or 6 described methods, the step 3) that it is characterized in that heating grinding mixture comprises puts into mixture 70 ℃ baking oven for heating, and grind once per half an hour, till no HAc emits.
As each described rare-earth doped beta-diketone class title complex among the claim 1-4 as the purposes of fluorescent material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516278A (en) * | 2011-12-19 | 2012-06-27 | 天津理工大学 | In situ ligand generated and ligand crystallized lanthanide complex and its preparation method |
| CN103013492A (en) * | 2011-09-26 | 2013-04-03 | 上海优你生物科技股份有限公司 | Nano-microsphere time resolution fluorescence probe as well as preparation method and use thereof |
| CN103374100A (en) * | 2013-07-12 | 2013-10-30 | 中科院广州化学有限公司 | Preparation and application of europium base polymer with long fluorescence lifetime and capable of selective recognition of anion |
| CN103694265A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
| CN103694993A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Beta-diketone rare earth complex red fluorescent material |
| CN103013492B (en) * | 2011-09-26 | 2016-12-14 | 上海溯源生物技术有限公司 | A kind of Nano microsphere time-resolved fluorescence probe and its production and use |
| CN113461505A (en) * | 2021-06-30 | 2021-10-01 | 湖北大学 | High-stability and volatile heteronuclear rare earth chelate as well as preparation method and application thereof |
| CN116814245A (en) * | 2023-07-07 | 2023-09-29 | 山东首明科技有限公司 | Composite material for manufacturing luminous plate and preparation method thereof |
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2004
- 2004-11-24 CN CN 200410084495 patent/CN1778786A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013492A (en) * | 2011-09-26 | 2013-04-03 | 上海优你生物科技股份有限公司 | Nano-microsphere time resolution fluorescence probe as well as preparation method and use thereof |
| CN103013492B (en) * | 2011-09-26 | 2016-12-14 | 上海溯源生物技术有限公司 | A kind of Nano microsphere time-resolved fluorescence probe and its production and use |
| CN102516278A (en) * | 2011-12-19 | 2012-06-27 | 天津理工大学 | In situ ligand generated and ligand crystallized lanthanide complex and its preparation method |
| CN102516278B (en) * | 2011-12-19 | 2014-07-23 | 天津理工大学 | In situ ligand generated and ligand crystallized lanthanide complex and its preparation method |
| CN103374100A (en) * | 2013-07-12 | 2013-10-30 | 中科院广州化学有限公司 | Preparation and application of europium base polymer with long fluorescence lifetime and capable of selective recognition of anion |
| CN103374100B (en) * | 2013-07-12 | 2015-06-10 | 中科院广州化学有限公司 | Preparation and application of europium base polymer with long fluorescence lifetime and capable of selective recognition of anion |
| CN103694265A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
| CN103694993A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Beta-diketone rare earth complex red fluorescent material |
| CN103694265B (en) * | 2013-12-31 | 2015-04-15 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
| CN113461505A (en) * | 2021-06-30 | 2021-10-01 | 湖北大学 | High-stability and volatile heteronuclear rare earth chelate as well as preparation method and application thereof |
| CN116814245A (en) * | 2023-07-07 | 2023-09-29 | 山东首明科技有限公司 | Composite material for manufacturing luminous plate and preparation method thereof |
| CN116814245B (en) * | 2023-07-07 | 2023-12-19 | 山东首明科技有限公司 | Composite material for manufacturing luminous plate and preparation method thereof |
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