CN102887915A - Heteronuclear bimetallic complex light-emitting material and preparation method and application thereof - Google Patents
Heteronuclear bimetallic complex light-emitting material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heteronuclear bimetallic complex light-emitting material. The invention also discloses a preparation method of the light-emitting material and application of the light-emitting material and aims at providing a material which is high in thermal stability, high in light stability and relatively high in light-emitting efficiency. The technical point is that the metal complex is provided with a structural formula which comprises an Al atom, an Eu atom, an 8-hydroxyquinoline and phenanthroline dual-ligand, two phenanthroline ligands and three dibenzoyl methane ligand, wherein the 8-hydroxyquinoline in the dual-ligand and the ligand 8-hydroxyquinoline are in coordination with a central atom Al together; and the phenanthroline dibenzoyl methane is in coordination with rare-earth metal europium. The heteronuclear bimetallic complex light-emitting material belongs to the technical field of light-emitting materials.
Description
Technical field
The present invention relates to a kind of luminescent material, specifically, is heteronuclear bimetal complexes luminescent material and preparation thereof and purposes, belongs to the material technology field of sending out.
Technical background
Luminescent material is widely used, all have important application in high-tech areas such as communication, satellite, radar, demonstration, record, optical computer, probe biomolecules, particularly the information age of today has promoted developing rapidly of luminescent material widely to the demand that various information show.
The application of luminescent material comprises the application of photoluminescence and electroluminescent two aspects: (1) photoluminescence is used, namely as fluorescent material.Luminescent material can be used as fluorescence dye, high-visibility pigment, fluorescent reagent, laser dyes etc., be widely used in the scintillator in fluorometric analysis, traffic sign, the nuclear technique, the fluorescent mark in fluorescence optical collector, bioanalysis and the medical diagnosis in the solar energy converting technology etc., have important application in fields such as industry, agricultural, biology, medical science, national defence.(2) electroluminescent is used, and namely luminescent layer and the charge transport layer as electroluminescent diode is applied to flat pannel display.
Luminescent material mainly is divided into phosphor and luminous organic material two large classes.The research that inorganics is luminous and application have had long history, but the shortcoming that phosphor exists some to be difficult to overcome: kind is few, and controllability is little, and working conditions is harsh, and energy efficiency is not high, is difficult to obtain blue light etc.Compare with phosphor, luminous organic material has obvious advantage, organic compound of a great variety, structure is varied, and can carry out molecular designing to organic compound as required, make it to satisfy various purposes, thereby the research of luminous organic material is subject to people's attention day by day in recent years.
Particularly since Bencini in 1985 finds that Gd (III) and Cu (II) interionic are the ferromegnetism exchange interaction in Gd (III)-Cu (II) heteronuclear complex molecule, caused that people study the interest of d-f heteronuclear title complex.In the d-f heteronuclear title complex since d metal ion and f metal ion interact often present be different from the equal double-core of rare earth and monokaryon rare earth compounding performance for the mechanism of action between the research metal-metal, design new molecular magnet, senser element, magnistor, light-converting material, the active centre of analogue enztme, the aspects such as research and development efficient catalyst have great importance and have thermal induction light transition function such as the triple helical configuration Ln (III) of Bunzli report-Fe (II) heteronuclear title complex, and the color of title complex and magnetic change with temperature change and has potential using value.Schiff bases is asymmetric is furnished with the machine luminescent material and can be divided into small molecules luminous organic material, metal complexes luminescent material and organic polymer luminescent material again.The small molecules luminous organic material has good film-forming properties, higher carrier mobility and thermostability preferably usually, easily obtain high purity product by distillation, but luminosity is not so good as metal complexes, and recrystallization easily occurs, and causes device stability to descend.Organic polymer luminescent material has higher second-order transition temperature usually, better heat stability, and also the El element manufacture craft is simpler, particularly easily makes broad area device, but the deficiency of its maximum is to be difficult to obtain high purity; The metal complexes luminescent material had then both possessed the advantage of the easy purification of small organic molecule and high fluorescence quantum efficiency, and usually have higher thermostability and a light stability, thereby be considered to a class luminescent material of tool application prospect, receive especially people's concern.
Summary of the invention
For the problems referred to above, the present invention discloses a kind of heteronuclear bimetal complexes luminescent material, the thermostability that this material is good, light stability and higher luminous efficiency.
Technical scheme of the present invention is such: a kind of heteronuclear bimetal complexes luminescent material, the structural formula of this this metal complexes are formula (1):
Formula (1).
In addition technical scheme of the present invention is such: the preparation method of this heteronuclear bimetal complexes luminescent material comprises the steps: successively
1) the synthetic two ligand L that contain oxine structure and phenanthroline structure
Under nitrogen protection, the amino phenanthroline of 5-and the 5-Formyl-8-hydroxyquinoline that in flask, add mol ratio 2～4:5, add again toluene, glacial acetic acid, then load onto the reflux condensing tube with calcium chloride tube, behind return stirring reaction 7～9h, filtered while hot with the hot toluene washing, is drying to obtain at 55～65 ℃;
2) monometallic aluminum complex LAlQ
2Synthetic
Take by weighing the synthetic oxine structure of the oxine of mol ratio 1:0.8～1.2 and step 1) and two ligand L of phenanthroline structure and be loaded in the flask, dissolve with DMF; After being dissolved in aluminum chloride in the methyl alcohol, be added drop-wise in the flask of two ligand L that oxine structure and phenanthroline structure are housed, heated and stirred backflow 3～5h is cooled to room temperature; With regulating pH value to 7.5～8.5, continue to stir 40～50min, to leave standstill, then centrifugation uses the methanol wash product extremely without chlorion, vacuum-drying, pulverulent solids is yellow monometallic aluminum complex LAlQ
2
3) target title complex Eu (DBM)
3LAlQ
2Synthetic
At first prepare EuCl
3, with Eu
2O
3Drop to the concentrated hydrochloric acid dissolving, be heated to 80 ℃ of near doing of evaporation, be cooled to room temperature, change in the 100 mL volumetric flasks, with dehydrated alcohol constant volume 0.01molL
-1, for subsequent use;
A certain amount of diphenylpropane-1,3-dione(DPPO) is dissolved in the dehydrated alcohol in 40-60 ℃, adds again a certain amount of step 2) synthetic LAlQ
2, after it dissolves fully, dripping gradually Eu
3+Ethanolic soln keeps Eu: DBM: LAlQ
2Molar ratio is 1: 3: 1, regulates p H value 6～7, until a large amount of safran precipitations occur, stirs 1～1.5 h, filters, and with volume ratio ethanol/water=1: 3 solution washing, vacuum-drying gets yellow solid Eu (DBM)
3LAlQ
2
Further, the preparation method of above-mentioned heteronuclear bimetal complexes luminescent material, it is characterized in that, the synthetic method of the amino phenanthroline of described 5-is: under nitrogen protection, add while stirring hydration phenanthroline and the vitriol oil of 2-3mol in dropping funnel, reflux condensing tube, temperature are housed take into account the there-necked flask of magnetic agitation, the two mixes, continue to stir, heat, slowly drip the mixture of the vitriol oil and concentrated nitric acid, heating, the control charge temperature; Back flow reaction 3.5～4.5h is cooled to room temperature with in the reaction solution impouring frozen water, regulates pH to 5.5～6.0, and yellow 5-nitro-1 is namely arranged, and the 1-phenanthroline is separated out; Suction filtration, washing, drying, again through ethyl alcohol recrystallization, drying gets the amino phenanthroline of faint yellow solid 5-.
Further; the preparation method of above-mentioned heteronuclear bimetal complexes luminescent material; it is characterized in that; the synthetic method of the amino phenanthroline of described 5-is: under nitrogen protection; dropping funnel is being housed; prolong; temperature is taken into account in the there-necked flask of magnetic agitation, and take 5 % Pd/ C-hydrazine hydrates as catalyzer, ethanol is solvent; when rising to 75 ℃, temperature adds rapidly 5-nitro-1; 10-phenanthroline ethanolic soln, water-bath refluxes a few hours, standing over night; reheat to 70 ℃; filtered while hot with washing with alcohol for several times, boils off ethanol with filtrate revolving; cooling; separate out yellow solid, suction filtration, vacuum-drying; ethyl alcohol recrystallization gets the amino phenanthroline of yellow needle-like crystal 5-.
Further, the preparation method of above-mentioned heteronuclear bimetal complexes luminescent material, described pH value is to regulating with ammoniacal liquor.
Further, the preparation method of above-mentioned heteronuclear bimetal complexes luminescent material, described pH value is to regulating with sodium hydroxide.
An in addition technical scheme of the present invention is like this: this heteronuclear bimetal complexes luminescent material is applied to the red light electroluminescent material.
This heteronuclear bimetal complexes luminescent material is applied to the luminescent layer in the electroluminescent device that the multilayer organic materials forms.
This heteronuclear bimetal complexes luminous material layer is applied to the electron transport material in the electroluminescent device that organic materials forms.
Inventive principle and advantage thereof: the objective of the invention is to obtain novel well behaved bimetal heteronuclear complex luminescent material, for this reason, at first a novel ligand L has been synthesized in design, this part is the combination of oxine structure and phenanthroline structure, two structures couple together by the C==N key, whole ligand molecular structure has larger conjugated system, contain simultaneously oxine structure and phenanthroline structure in the molecule, compare the quinoline structure, phenanthroline structure of many introducings in the molecule, thereby this title complex should have higher electron affinity than quinoline, possesses better electronic injection and transport properties.While 1, the 10-phenanthroline is as important part, and its two adjacent nitrogen-atoms can form d-π back donating bondings with many transition metal, obtain title complex stable and that luminescent properties is good, with gained part and Al
3+And Eu
3+Carry out coordination, obtained a kind of novel europium aluminium heteronuclear bimetal complexes luminescent material, show through NMR, mass spectrum, ultimate analysis and ray crystallographic analysis, this title complex has following molecular structure:
In the part oxine part and part oxine (Q) together with central atom Al coordination, the phenanthroline part is as Ligands, with the first part diphenylpropane-1,3-dione(DPPO) (DBM) and Rare Earth Europium coordination, formed and both contained classical aluminum complex, contained again the heteronuclear bimetal complexes (Eu (DBM) of classical europium complex
3LAlQ
2).This title complex has good solubility in common are the machine solvent, such as tetrahydrofuran (THF), chloroform, toluene etc.; This title complex has good thermal characteristics, and fusing point surpasses 300 ℃, and initial heat decomposition temperature surpasses 350 ℃, and does not have other obvious heat deflections before fusing point, and this is very favorable for obtaining good device performance, and is conducive to vacuum plating.Be E through its initial oxidation current potential of cyclic voltammetry and in conjunction with the HOMO energy level that the band edge wavelength of its ultra-violet absorption spectrum can calculate this title complex
HOMO=-6.18eV; Its lumo energy is E
LUMO=3.08eV, (2.4 ~ 2.65eV) is higher, illustrates that the injection energy barrier between this title complex and negative electrode is less, can be used as electron transport material than electron transport material quinoline commonly used in the OLED device.The fluorescence spectrum of this title complex under solution state produces the characteristic emission of Eu (III) ion, is red illuminating material, and its luminous quantum efficiency in solution is than monometallic title complex Eu (DBM)
3The height of Phen.In a word, title complex Eu (DBM)
3LAlQ
2Have preferably monochromaticity and higher luminous efficiency as the red emission material, add its unique coordination structure, become very promising electroluminescent material.
Description of drawings
Fig. 1 is title complex Eu of the present invention (DBM)
3LAlQ
2The TG curve;
Fig. 2 is title complex Eu of the present invention (DBM)
3LAlQ
2The DSC curve;
Fig. 3 is title complex Eu of the present invention (DBM)
3LAlQ
2The CV curve;
Fig. 4 is title complex Eu of the present invention (DBM)
3LAlQ
2The UV-vis curve;
Fig. 5 is title complex Eu of the present invention (DBM)
3LAlQ
2The solution fluorescence spectrum.
Specific embodiments
In order to illustrate that better the present invention, the below enumerate some preferred specific embodiments, but content of the present invention not only is confined to cited embodiment.
Metal complexes of the present invention synthetic is divided into two steps: the one, contain two ligands synthetic of oxine structure and phenanthroline structure, and the 2nd, the target Complex synthesis.
Implementation step one: the synthetic two ligands that contain oxine structure and phenanthroline structure
In the first step, comprise the synthetic of 3 intermediates: the amino phenanthroline of 5-Formyl-8-hydroxyquinoline, 5-nitro phenanthroline and 5-.
(1) intermediate compound 5-Formyl-8-hydroxyquinoline is synthetic:
Under nitrogen protection; in reaction flask, add oxine 6g(100mmo l); ethanol 25 mL, sodium hydroxide solution (13g sodium hydroxide+16 mL distilled water) stirs lower back flow reaction; after the reaction; slightly cold, add phase-transfer catalyst, slowly drip again chloroform 8mL; drip and finish, continue reaction 13 h.Vacuum is steamed except chloroform and ethanol, residuum is poured in the 125mL water, uses the dilute hydrochloric acid acidifying, has the soil Red precipitation to generate, suction filtration, with sherwood oil extracting 10h, yellow solid, drying are separated out in the extract cooling after the filter cake vacuum-drying, use again the dehydrated alcohol recrystallization, get safran solid 2.1g, productive rate is 28%, and fusing point is 172
oC;
1H NMR (300MHz, CDCl
3): δ=10.18 (d, 1H), 8.25 (s, 1H), 8.13 (d, 1H), 7.50 (m, 1H), 8.49 (d, 1H), (7.69 d, 1H), 7.26 (d, 1H), MS (m/z): 173 (M)
+, ultimate analysis (%): C, 69.48, H, 4.249, N, 8.11, calculated value (%, C
10H
7NO
2): C, 69.42, H, 4.246, N, 8.05;
(2) intermediate compound 5-nitro phenanthroline is synthetic:
Under nitrogen protection, in dropping funnel, reflux condensing tube, temperature are housed take into account the there-necked flask of magnetic agitation, add while stirring 5.0 g hydration phenanthrolines and the 75 mL vitriol oils, the two is mixed, continue to stir, be heated to 110 oC, slowly drip the mixture of the 250 mL vitriol oils and concentrated nitric acid, heating, the control charge temperature is no more than 170 oC; Back flow reaction 4 h are cooled to room temperature with in the reaction solution impouring frozen water, regulate about pH to 6.0 with the sodium hydroxide solution of 10 %, and yellow 5-nitro-1 is namely arranged, and the 1-phenanthroline is separated out; Suction filtration, washing, drying, again through ethyl alcohol recrystallization, drying gets faint yellow solid 5.2g.Productive rate 91 % (with 1,1 0-phenanthroline meter).Surveying its fusing point is 201.6 ~ 201.7 oC;
1H NMR (300MHz, CDCl
3): 874 (m, the 2H) of δ=7.770～7., 8.425～8.437 (q, 1H), 8. 710 (s, 1H), 9.020 ~ 9. 070 (q, 1H), 9.339～9.384 (m, 2H); MS (m/z): 224. 1[(M+1)
+]; Ultimate analysis (%): C, 75.30; H, 4.05; N, 6.24; Calculated value (%, C
14H
9NO
2): C, 75.33; H, 4.06; N, 6.27;
(3) the amino phenanthroline of intermediate compound 5-is synthetic:
Under nitrogen protection, being housed, dropping funnel, prolong, temperature take into account in the there-necked flask of magnetic agitation, and take 5 % Pd/ C-hydrazine hydrates as catalyzer, 75mL ethanol is solvent, carries out reduction reaction.When rising to 75 ℃, temperature adds rapidly 2.5g 5-nitro-1,10-phenanthroline ethanolic soln, and water-bath refluxes a few hours, standing over night.Reheat to 70 ℃, filtered while hot, with washing with alcohol for several times.Filtrate revolving boiled off most of ethanol, and yellow solid is separated out in cooling, suction filtration, and vacuum-drying, ethyl alcohol recrystallization gets yellow needle-like crystal 2g.Productive rate is 90%.Surveying its fusing point is 258 ~ 259oC;
1H NMR (300MHz, CDCl
3): δ=3.310 ~ 3.332 (m, 2H), 6.956 (s, 1H), 7.479 ~ 7.691 (m, 2H), 7.971 ~ 8.016 (d, 1H), 8.262 ~ 8.319 (d, 1H), 8.941 ~ 9.216 (m, 2H), MS (m/z): 193 (M)
+, ultimate analysis (%): C, 87.05, H, 5.70, N, 7.25, calculated value (%, C
14H
11N): C, 87.01; H, 5.73; N, 7.26;
(4) target ligand is synthetic: the two ligands (L) that contain oxine structure and phenanthroline structure
Under nitrogen protection; in flask, add the amino phenanthroline of 0.58g (3mmol) 5-and 0.52g(5mmol) 5-Formyl-8-hydroxyquinoline, 180mL toluene, 3mL glacial acetic acid; then load onto the reflux condensing tube with calcium chloride tube; behind the return stirring reaction 8h, filtered while hot is with hot toluene washing 4 times; dry about 60 ℃; get the orange crystal of 0.97g, productive rate is 92%, and fusing point is 250 oC.
1H?NMR(300MHz,?CDCl
3):?δ=5.351(s,1H),?7.268(d,1H),
(7.611 m, 1H), 7.581 (m, 1H), 7.892 (d, 1H), 8.385 (d, 1H), 8.636 (s, 1H), 8.826 (s, 1H), 8.882 (d, 1H), MS (m/z): 350 (M)
+, ultimate analysis (%): C, 75.41, H, 4.02, N, 15.90, calculated value (%, C
22H
14N
4O): C, 75.42, H, 4.03, N, 15.99;
Implementation step two: target title complex Eu (DBM)
3LAlQ
2Synthetic
In second step, be divided into two steps, at first to the part of the oxine in two ligands and Al
3+The monometallic aluminum complex is synthesized in coordination, and then the monometallic aluminium that will contain the phenanthroline structure joins thing as Ligands, adds the first ligand DBM, generates target heteronuclear bimetal complexes Eu (DBM) with Eu (III) coordination
3LAlQ
2
(1) monometallic aluminum complex LAl Q
2Synthetic
Take by weighing 0.29 g oxine, 0.35g ligand L in flask, with 20mL DMF dissolving, after in the molten 10mL methyl alcohol of 0.48 g aluminum chloride, be added drop-wise in the last solution, heated and stirred backflow 4h is cooled to room temperature.Regulate about pH value to 8 with the weak ammonia that is about 5 mol/L, slowly drip ammoniacal liquor, note observe phenomena, when a dropping ammoniacal liquor, find flaxen precipitation can occur at the bottle wall, then continue to be added drop-wise to pH and be about at 8 o'clock, continue to stir 45min, leave standstill a few hours, then centrifugation, with the methanol wash product to without chlorion, vacuum-drying, pulverulent solids are yellow, and 0.42g weighs, productive rate is 80%, m.p.〉300
oC.
1H?NMR(300MHz,?CDCl
3):?δ=7.035?(s,1H),?7.273(s,1H),
(7.584 m, 1H), 7.615 (m, 1H), 7.642 (m, 1H), 7.985 (d, 1H), 8.386 (s, 1H), 8.826 (d, 1H), 8.892 (d, 1H), MS (m/z): 520 (M)
+, ultimate analysis (%): C, 71.51, H, 3.69, Al, 5.19, N, 13.50, calculated value (%, C
31H
19AlN
5O
2): C, 71.53; H, 3.68; Al, 5.18; N, 13.46;
(2) target title complex Eu (DBM)
3LAlQ
2Synthetic
At first prepare EuCl
3, with 1mmolEu
2O
3With the dissolving of 50mL concentrated hydrochloric acid, near the doing of heating in water bath to 80 ℃ evaporation is cooled to room temperature, changes in the 100 mL volumetric flasks, with dehydrated alcohol constant volume (0.01molL
-1), for subsequent use.
A certain amount of DBM is dissolved in the dehydrated alcohol in 50 ℃, adds again a certain amount of LAlQ
2, after it dissolves fully, with Eu
3+Ethanolic soln dropwise adds mentioned solution, keeps Eu: DBM: LAlQ
2Molar ratio is 1: 3: 1, regulates p H=6～7, until a large amount of safran precipitations occur, stir about 1.5 h filter, and use ethanol/water=1: the 3(volume ratio) solution washing, and vacuum-drying gets yellow solid, productive rate 85%; M.p.〉300
oC.
1HNMR (300MHz, CDCl
3): δ=7.034 (s, 1H), 7.271 (s, 1H), 7.341 (m, 1H), 7.412 (m, 1H), 7.582 (m, 1H), (7.625 m, 1H), 7.643 (m, 1H), 7.778 (m, 1H), 7.896 (m, 1H), 7.985 (d, 1H), 8.385 (s, 1H), 8.828 (d, 1H), 8.892 (d, 1H), MS (m/z): 896 (M)
+, ultimate analysis (%): C, 61.67, H, 3.39, Al, 3.03, Eu, 16.97, N, 7.84, calculated value (%, C
46H
30AlEuN
5O
4): C, 61.68, H, 3.38, Al, 3.01, Eu, 16.97, N, 7.82;
Target compound has been carried out a series of performance test, such as thermal characteristics, chemical property, ultraviolet and fluorescence property.TG(accompanying drawing 1) and DSC(accompanying drawing 2) test show that material of the present invention has preferably thermostability, its initial decomposition temperature reaches more than 300 ℃, before its fusing point without other obvious heat deflections.Cyclic voltammetry (accompanying drawing 3) shows that material of the present invention also has preferably chemical property, and can be calculated the HOMO energy level is E
HOMO=-6.18eV; Its lumo energy is E
LUMO=3.08eV, material of the present invention has been carried out ultraviolet (accompanying drawing 4) and fluorescence (accompanying drawing 5) performance test at THF solution, and the result shows, material of the present invention is a kind of red light luminescent material, its fluorescence spectrum peak value shows as the characteristic emission of Eu (III) ion, sees accompanying drawing 5.
Claims (9)
1. a heteronuclear bimetal complexes luminescent material is characterized in that, the structural formula of this metal complexes is formula (1):
Formula (1).
2. the preparation method of heteronuclear bimetal complexes luminescent material claimed in claim 1 is characterized in that, comprises the steps: successively
1) the synthetic two ligands that contain oxine structure and phenanthroline structure
Under nitrogen protection, the amino phenanthroline of 5-and the 5-Formyl-8-hydroxyquinoline that in flask, add mol ratio 2～4:5, add again toluene, glacial acetic acid, then load onto the reflux condensing tube with calcium chloride tube, behind return stirring reaction 7～9h, filtered while hot with the hot toluene washing, is drying to obtain at 55～65 ℃;
2) monometallic aluminum complex LAlQ
2Synthetic
Take by weighing the synthetic oxine structure of the oxine of mol ratio 1:0.8～1.2 and step 1) and two ligands of phenanthroline structure and be loaded in the flask, dissolve with DMF; After being dissolved in aluminum chloride in the methyl alcohol, be added drop-wise in the flask of two ligands that oxine structure and phenanthroline structure are housed, heated and stirred backflow 3～5h is cooled to room temperature; With regulating pH value to 7.5～8.5, continue to stir 40～50min, to leave standstill, then centrifugation uses the methanol wash product extremely without chlorion, vacuum-drying, pulverulent solids is yellow monometallic aluminum complex LAlQ
2
3) target title complex Eu (DBM)
3LAlQ
2Synthetic
At first prepare EuCl
3, with Eu
2O
3Drop to the concentrated hydrochloric acid dissolving, be heated to 80 ℃ of near doing of evaporation, be cooled to room temperature, change in the 100 mL volumetric flasks, with dehydrated alcohol constant volume 0.01molL
-1, for subsequent use; A certain amount of diphenylpropane-1,3-dione(DPPO) is dissolved in the dehydrated alcohol in 40～60 ℃, adds again a certain amount of step 2) synthetic LAlQ
2, after it dissolves fully, dripping gradually Eu
3+Ethanolic soln, keep Eu: DBM: the LAlQ2 molar ratio is 1: 3: 1, regulates p H value 6～7, until a large amount of safran precipitations occur, stirs 1～1.5 h, filter, washing, vacuum-drying gets yellow solid Eu (DBM) 3LAlQ2.
3. the preparation method of heteronuclear bimetal complexes luminescent material according to claim 2, it is characterized in that, the synthetic method of the amino phenanthroline of described 5-is: under nitrogen protection, add while stirring hydration phenanthroline and the vitriol oil of 2～3mol in dropping funnel, reflux condensing tube, temperature are housed take into account the there-necked flask of magnetic agitation, the two mixes, and continues to stir, heating, slowly drip the mixture of the vitriol oil and concentrated nitric acid, heating, control charge temperature; Back flow reaction 3.5～4.5h is cooled to room temperature with in the reaction solution impouring frozen water, regulates pH to 5.5～6.0, and yellow 5-nitro-1 is namely arranged, and the 1-phenanthroline is separated out; Suction filtration, washing, drying, again through ethyl alcohol recrystallization, drying gets the amino phenanthroline of faint yellow solid 5-.
4. the preparation method of heteronuclear bimetal complexes luminescent material according to claim 2; it is characterized in that; the synthetic method of the amino phenanthroline of described 5-is: under nitrogen protection; dropping funnel is being housed; prolong; temperature is taken into account in the there-necked flask of magnetic agitation; take 5 % Pd/ C-hydrazine hydrates as catalyzer; ethanol is solvent, adds rapidly 5-nitro-1,10-phenanthroline ethanolic soln when temperature rises to 75 ℃; water-bath refluxes a few hours; standing over night reheats to 70 ℃ filtered while hot; with washing with alcohol for several times; filtrate revolving boiled off ethanol, and yellow solid is separated out in cooling; suction filtration; vacuum-drying, ethyl alcohol recrystallization gets the amino phenanthroline of yellow needle-like crystal 5-.
5. the preparation method of heteronuclear bimetal complexes luminescent material according to claim 2 is characterized in that, described pH value is to regulating with ammoniacal liquor.
6. the preparation method of heteronuclear bimetal complexes luminescent material according to claim 3 is characterized in that, described pH value is to regulating with sodium hydroxide.
7. the purposes of heteronuclear bimetal complexes luminescent material claimed in claim 1 is characterized in that, is applied to the red light electroluminescent material.
8. heteronuclear bimetal complexes luminescent material claimed in claim 1 is characterized in that, is applied to the luminescent layer in the electroluminescent device that the multilayer organic materials forms.
9. heteronuclear bimetal complexes luminous material layer claimed in claim 1 is characterized in that, is applied to the electron transport material in the electroluminescent device that organic materials forms.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104270847A (en) * | 2014-10-30 | 2015-01-07 | 中国科学院长春应用化学研究所 | White organic light-emitting device and preparation method thereof |
| CN108129505A (en) * | 2018-01-26 | 2018-06-08 | 河北工业大学 | A kind of fluorescent material of aluminium organic coordination compound and its graphene oxide doped aluminium organic coordination compound |
| CN111234254A (en) * | 2020-02-27 | 2020-06-05 | 西北大学 | D-p heteronuclear bimetallic organic framework material capable of realizing white light emission and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718668A (en) * | 2005-07-06 | 2006-01-11 | 太原理工大学 | Preparation method of organic electro luminous material rare earth europium organic metal complex |
| TW200613313A (en) * | 2004-06-15 | 2006-05-01 | Nissan Chemical Ind Ltd | Rare earth metal complex light-emitting material having aromatic organic ligand |
| CN101159315A (en) * | 2007-11-06 | 2008-04-09 | 中国科学院长春应用化学研究所 | Red organic electroluminescent device and method for fabricating the same |
| CN101367826A (en) * | 2008-09-24 | 2009-02-18 | 上海大学 | Linking type Eu3+ organic conjunction, its copolymer red luminescent material and method of preparing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200613313A (en) * | 2004-06-15 | 2006-05-01 | Nissan Chemical Ind Ltd | Rare earth metal complex light-emitting material having aromatic organic ligand |
| CN1718668A (en) * | 2005-07-06 | 2006-01-11 | 太原理工大学 | Preparation method of organic electro luminous material rare earth europium organic metal complex |
| CN101159315A (en) * | 2007-11-06 | 2008-04-09 | 中国科学院长春应用化学研究所 | Red organic electroluminescent device and method for fabricating the same |
| CN101367826A (en) * | 2008-09-24 | 2009-02-18 | 上海大学 | Linking type Eu3+ organic conjunction, its copolymer red luminescent material and method of preparing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104270847A (en) * | 2014-10-30 | 2015-01-07 | 中国科学院长春应用化学研究所 | White organic light-emitting device and preparation method thereof |
| CN108129505A (en) * | 2018-01-26 | 2018-06-08 | 河北工业大学 | A kind of fluorescent material of aluminium organic coordination compound and its graphene oxide doped aluminium organic coordination compound |
| CN111234254A (en) * | 2020-02-27 | 2020-06-05 | 西北大学 | D-p heteronuclear bimetallic organic framework material capable of realizing white light emission and preparation method thereof |
| CN111234254B (en) * | 2020-02-27 | 2021-07-27 | 西北大学 | D-p heteronuclear bimetallic organic framework material capable of realizing white light emission and preparation method thereof |
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