CN1687080A - Rare earth complexes chelated by aromatic base substituted diphosphine dioxide and its synthesizing process - Google Patents
Rare earth complexes chelated by aromatic base substituted diphosphine dioxide and its synthesizing process Download PDFInfo
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Abstract
The present invention relates to a kind of high-performance photoelectric function rare earth complex material and its preparation method. Said invention uses substituted diphosphine dioxide containing aromatic group as ligand, and utilizes complexation reaction to synthesize a series of high-effective rare earth photoelectric function complexes, and prepares doped red electroluminescent device containing above-mentioned rare earth photoelectric function material, said electroluminescent device can obtan satisfactory result in the luminance, current density and efficiency under the high current density.
Description
Technical field
The invention belongs to the organic electronic functional material technical field, be specifically related to a class diphenylphosphine derivative aromatic base and replace diphosphine dioxide rare earth compounding and synthetic method and application.
Technical background
In more than ten years, photoelectric information functional material has obtained paying close attention to widely and studying as the type material with broad prospect of application in the past.Again to solar cell, scientists has all been carried out extensive studies from the organic electroluminescent to the organic laser.Rare earth photoelectricity functional material has been because its unique character and remarkable photoelectric characteristic have obtained great concern in this field, and shows the not available plurality of advantages of other materials in many aspects.Aspect organic electroluminescent, organic electroluminescent LED (OLEDs) is owing to its potential application in indicating meter of new generation and lighting engineering causes extensive attention.Yet, now still there are some important challenges, comprise the maximization of external quantum efficiency (EQE), the design of the novel material that purity of color is higher is with synthetic etc.In general, organic molecule and organic macromolecular LED material are owing to the characteristic of itself, and the glow peak peak width at half height is generally at 50～100nm, purity of color is not high, and the luminous peak width at half height of rare earth electroluminescent material is about 10nm, and it is luminous to present the arrowband, helps realizing the high color purity display device.The luminous efficiency of rare earth electroluminescent material can reach 100% in theory, but need obtain more effectively transmission ofenergy from ligand molecular, the while ligand molecular has suitable electric charge injection and transmission performance just may promote that rare earth atom more effectively obtains energy, and then improves luminous efficiency.
The stability of rare earth material electroluminescent device also is that one of this area has problem to be solved, and we attempt making its stability in device obtain certain raising by the optimised devices structure.
Triphenylphosphine and oxide compound thereof are widely used in fields such as chemical reaction catalysis, organic electroluminescent as the neutral ligand material, it cooperates the material that obtains to have goodish electroluminescent properties as neutral ligand with rare earth element.Wherein, be typically Eu (TTA)
3(TPPO)
2, wherein, TTA is a thienyl trifluoromethyl diketone, TPPO is a triphenylphosphine oxidation thing.Because the coordination by two triphenylphosphine oxides realizes center trivalent europium ion (Eu
3+) eight-coordinate, the effect of seeing these two parts from the angle of molecular structure only is saturated Eu
3+The ligancy of central ion, limited to the injection and the transmission contribution of current carrier, so it is generally acknowledged 1,10-phenanthrolene derivative is more suitable for as the electroluminescent part than phosphine oxygen class title complex, and it not only can saturated Eu
3+Ligancy, and can play the effect that strengthens electric transmission and injection.But in fact be expected to obtain coordination ability and carrier transport ability meets or exceeds 1, the phosphine oxygen class title complex of 10-phenanthrolene derivative by molecular designing.
Summary of the invention
The objective of the invention is to use aromatic base to replace the synthetic class novel rare-earth photoelectric functional material of diphosphine dioxide ligand material, and design suitable device architecture, preparation contains above-mentioned rare earth photoelectricity functional material doping type electroluminescent device.
See that from the angle of molecular designing aromatic base replaces diphosphine dioxide and not only has and 1, electric transmission that 10-phenanthrolene derivative is similar and injection effect, and also functionalization is convenient.Therefore the present invention has used a class aromatic base to replace diphosphine dioxide, and has made the novel rare-earth photoelectric functional material that a class has higher luminescent properties with this compounds as the neutral ligand material.With respect to similar triphenylphosphine oxidation thing (TPPO), the bitooth ligand material that uses among the present invention has fundamentally solved existing three problems of TPPO aspect electroluminescent: solve the problem that loose complex structure causes forming exciplex 1..Aromatic base replaces diphosphine dioxide bitooth ligand material owing to having the function corresponding group to link to each other between two points of engagement to make the energy can uniform distribution in whole complexes system, thereby has avoided the generation of exciplex; 2. the current carrier that improves neutral ligand injects and transmittability.Aromatic base replaces diphosphine dioxide bitooth ligand material and has bigger conjugate planes and conjugate length, has improved the injection efficiency of current carrier, has also correspondingly improved the transmittability of current carrier simultaneously; 3. improve the stability of title complex, guarantee device stable photoelectric properties of performance under long-time use and action of high voltage.Aromatic base replaces diphosphine dioxide bitooth ligand material and has given whole title complex inflexible structure more, has improved the thermostability and the spectrum stability of title complex.Be reflected on the device performance, we can see that from accompanying drawing device has extremely stable spectrum at 7V in the voltage range of 25V.Chromatogram stability under high-voltage has reflected that from a side such functional materials has quite long work-ing life.
To sum up, aromatic base replaces diphosphine dioxide bitooth ligand material not only can improve the rare earth compounding stability of structure, and can reduce effectively and form swash matrix composite and cause De temper effect and the Rong Ji temper effect of going out of going out, improve luminous efficiency, obtain the higher luminescent device of purity of color, thermal stability also obtains suitable improvement simultaneously, thereby can improve the over-all properties of rare earth electroluminescent device.When being used for electroluminescent device, obtained gratifying result aspect the efficient of the device of making under brightness, current density and high current density, its over-all properties reaches even is better than present known rare earth and cooperates electroluminescent material, thereby has obtained the rare earth photoelectricity functional material that a class has wide application prospect.
Below content of the present invention is further described in detail:
The aromatic base that the present invention proposes replaces the diphosphine dioxide huge legendary turtle and closes rare earth compounding, and its central ion is a rare earth ion, is obtained through complex reaction by two kinds of parts, and its basic structure formula is as follows:
Wherein, Ar
1, Ar
2And Ar
3Be respectively the group that contains heteroatomic aromatic hydrocarbons, aromatic hydrocarbons or alkylaromatic hydrocarbon, and contain the derivative of alkyl, haloalkyl, aryl, halogenated aryl, halogen or alkylaromatic hydrocarbon group;
R
1, R
2And R
3Be respectively the group that contains alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; Comprising: thienyl trifluoromethyl methyl ethyl diketone, phenylbenzene methyl ethyl diketone, methyl ethyl diketone and other beta-diketon class commonly used and other types of ligands.
RE is a central ion, specifically can be rare earth ion, as rare earth ions such as lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, gadolinium, dysprosium, holmium, terbium, erbium, thulium, ytterbium or lutetiums.
The invention allows for above-mentioned is the synthetic method of the rare earth compounding of part with aromatic base replacement diphosphine dioxide.It as solvent, makes rare earth ion and following first, second part generation complex reaction form title complex with alcohol under reflux temperature, and wherein first part is an anion ligand, and second part is a neutral ligand, and concrete operations are as follows:
Get three normal first parts and be dissolved in the ethanol, 50～70 ℃ of aqueous sodium hydroxide solution neutralizations that drip equivalent down, the reaction times is 15～60 minutes;
Get the inorganic salt of rare earth of monovalent or rare earth organic compounds is water-soluble or organic solvent and dropping in the system, temperature is controlled at 70～80 ℃, reacts 30～60 minutes;
Second part of getting monovalent is dissolved in ethanol and drops in the system, and temperature maintenance is at 70～80 ℃, and the reaction times is 2～4 hours;
In the above-mentioned synthesis step, first part of employing is the beta diketone class, and the structure of this compound is as follows:
Wherein, R
1, R
2And R
3Be respectively the group that contains alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon; Comprising: thienyl trifluoromethyl methyl ethyl diketone, phenylbenzene methyl ethyl diketone, methyl ethyl diketone and other beta-diketons commonly used.
Second part that adopts is that aromatic base replaces diphosphine dioxide, and the molecular structure of this compound is as follows:
Wherein, Ar
1, Ar
2And Ar
3Be respectively the group that contains heteroatomic aromatic hydrocarbons, aromatic hydrocarbons or alkylaromatic hydrocarbon, and contain the derivative of alkyl, haloalkyl, aryl, halogenated aryl, halogen or alkylaromatic hydrocarbon group.
In the aforesaid method, replace the synthetic of diphosphine dioxide for the second part aromatic base, concrete operations are as follows:
(1) works as Ar
2And Ar
3During for phenyl, use diphenyl phosphine chloride as phosphonate reagent;
Get monovalent Ar
1Bromide is dissolved in anhydrous diethyl ether or tetrahydrofuran (THF), and solvent need be handled through anhydrous and oxygen-free.Drip two normal n-Butyl Lithiums down at-78～0 ℃, reacted 1～2 hour, at room temperature reacted then 0.5～1 hour;
System is reduced to-78～0 ℃, slowly drip diphenyl phosphine chloride ether or tetrahydrofuran solution, reacted 2-3 hour; At room temperature reacted then 8～24 hours, and obtained aromatic base and replace two phosphine things;
Be dissolved in top two phosphine things in the dioxane equal solvent and drip 1.5 normal hydrogen peroxide oxidations, at room temperature reacted 2～4 hours, promptly obtain aromatic base and replace diphosphine dioxide.
Wherein, Ar
1Bromide replaces and when having reactive hydrogen on adjacent aromatic rings, can add the N of equivalent for single, N, and N ', N '-tetramethyl-ethyl diamines increases lithiation speed and productive rate.Ar
1Bromide then need not add during for two bromo.
(2) work as Ar
2And Ar
3During for the distinct fragrance group, using phosphorus trichloride as phosphonate reagent, is solvent with anhydrous diethyl ether or tetrahydrofuran (THF), is progressively adding Ar under-78～0 ℃ in 3.5 normal phosphorus trichlorides
2And Ar
3Lithium for thing, keep phosphorus trichloride excessive; With the phosphonate reagent system that obtains, drop to the Ar of monovalent
1React in the ether of lithiumation thing or the tetrahydrofuran solution, the phosphine thing that reaction is obtained promptly obtains aromatic base and replaces diphosphine dioxide with 1.5 normal hydrogen peroxide oxidations.
Synthetic method according to above-mentioned two kinds of aromatic bases replacement diphosphine dioxide parts that provide can obtain following two kinds of typical parts.Promptly work as Ar
1Be phenylate, two phosphorus atom replace Ar respectively on the ortho position of two phenyl
2, Ar
3During for phenyl, obtain second part 2,2 '-diphenylphosphine oxygen base phenylate, its structural formula is shown in (IV).
Work as Ar
1Be naphthyl, two phosphorus atom are gone up replacement, Ar at 1,8 of two naphthyls respectively
2, Ar
3During for phenyl, obtain second ligand 1,8-diphenylphosphine oxygen base naphthalene, its structural formula is shown in (V).
According to the synthetic method of above-mentioned title complex, can obtain following 4 kinds of typical title complexs.Promptly working as the center ion is trivalent europium ion (Eu
3+), first part is a thienyl trifluoromethyl methyl ethyl diketone, second part is 2, during 2 '-diphenylphosphine oxygen base phenylate, obtains title complex (VI); When first part is the phenylbenzene methyl ethyl diketone, second part is 2, during 2 '-diphenylphosphine oxygen base phenylate, obtains title complex (VII); When first part is a thienyl trifluoromethyl methyl ethyl diketone, second ligand 1 during 8-diphenylphosphine oxygen base naphthalene, obtains title complex (VIII); When first part is the phenylbenzene methyl ethyl diketone, second ligand 1 during 8-diphenylphosphine oxygen base naphthalene, obtains title complex (IX).
The present invention also provides with such rare earth compounding as the application of electroluminescent material in a class ruddiness device.Concrete steps are as follows: at first make conductive layer, vacuum evaporation hole mobile material on conductive layer then, the adulterated luminescent layer of the aforesaid rare earth compounding of evaporation again, evaporation electric transmission hole barrier materials on it, follow the evaporation electron transfer layer, last evaporation second layer conductive layer.
The first layer conductive layer preferably is produced on the substrate, and substrate is generally glass or plastics.
The first layer conductive layer is an anode, and second layer conductive layer is a negative electrode.Negative electrode preferably is made of the metal or the semi-transparent conductor that can produce reflection, is generally calcium, magnesium, aluminium, silver and alloy thereof, is preferably in its surface when using aluminium and plates one deck LiF.Anode preferably (as polyaniline, PANI) is made of tin indium oxide (ITO) or transparent conductive polymer.
One deck hole transmission layer is arranged between the first layer conductive layer and luminescent layer, between electric transmission/hole blocking layer and the second layer conductive layer one deck electron transfer layer is arranged preferably; Luminescent layer is between hole transmission layer and electric transmission/hole blocking layer, and luminescent layer can be aforesaid any rare earth compounding and 4,4 '-N, the adulterate body of N '-carbazyl biphenyl (CBP).
Device anode among the present invention is made on residuites such as glass or plastics by evaporation by tin indium oxide (ITO) or polyaniline (PANI).Negative electrode preferably constitutes (thickness is 1000nm/10nm) by aluminium/lithium fluoride (Al/LiF).
The anodic hole is injected and the electronics of transmission and negative electrode injects and transmission in order to improve, and makes charge energy compound well at luminescent layer, can adopt hole transmission layer, electric transmission, hole transport/electronic barrier layer and electric transmission/hole blocking layer.
The thickness of hole transport layer film is 20～60nm, can pass through vacuum thermal evaporation technology film forming on anode.
Luminescent layer is rare earth luminous title complex and 4,4 '-N, and the adulterate body of N '-carbazyl biphenyl (CBP), film thickness is 10-100nm, can deposit on the hole transmission layer by coevaporation method.
The film thickness of electron transfer layer is 10～80nm, and preferably 20～50nm according to the difference of electric transmission layer material, can deposit to it on electric transmission/hole blocking layer by thermal evaporation.
The thickness of electric transmission/hole barrier layer film is 10～80nm, deposits on the luminescent layer by thermal evaporation techniques.
Description of drawings
Fig. 1. with synthetic rare earth compounding Eu (TTA) among the present invention
3The Ultraluminescence spectrum spectrogram of (DPEphos Oxide)
Fig. 2. with synthetic rare earth compounding Eu (TTA) among the present invention
3The Ultraluminescence spectrum spectrogram of (Naphos Oxide)
Fig. 3. with synthetic rare earth compounding Eu (TTA) among the present invention
3The thermogravimetric analysis spectrogram of (DPEphos Oxide)
Fig. 4. with synthetic rare earth compounding Eu (TTA) among the present invention
3The differential scanning analysis of spectra of (DPEphos Oxide)
Fig. 5. with synthetic rare earth compounding Eu (TTA) among the present invention
3The thermogravimetric analysis spectrogram of (Naphos Oxide)
Fig. 6. with synthetic rare earth compounding Eu (TTA) among the present invention
3The differential scanning analysis of spectra of (Naphos Oxide)
Fig. 7. with synthetic rare earth compounding Eu (TTA) among the present invention
3The voltage-to-current relation and the voltage-brightness relationship curve of the ruddiness device that (DPEphos Oxide) makes
Fig. 8. with synthetic rare earth compounding Eu (TTA) among the present invention
3Electroluminescent spectrogram under the different voltages of the ruddiness device that (DPEphos Oxide) makes
Embodiment
In order to understand content of the present invention better, further specify technical scheme of the present invention below by embodiment and legend.
Room temperature N
2To dissolve with tetrahydrofuran (THF) in 32ml (1.6M) n-Butyl Lithium (n-BuLi) and 6.0g (51.2mmol) tetramethyl-Edamine (TMEDA) the adding two neck bottles under the atmosphere, stir a moment, drip 4g (23.5mmol) phenylate/15ml tetrahydrofuran solution, reaction is spent the night; Extract 9.8ml (54.6mmol) diphenyl phosphine chloride (Ph with syringe
2PCl) to be added dropwise in the system after the dilution of 15ml normal hexane, white precipitate occurs, reaction is spent the night.System adds methylene chloride and the water stratification extraction, and the organic phase drying is spin-dried for, and product obtains white solid with washing with acetone.
1H?NMR(CDCl
3)：7.310-7.389(13H)，7.223-7.290(2H)，7.101-7.192(8H)，6.995-7.064(2H)，6.670-6.736(2H)，6.565-6.631(2H)。
With 0.527g (1mmol) 2,2 '-diphenylphosphine phenylate (DPEphos) adds in the two neck bottles, with 30ml1 under the room temperature, the dissolving of 4-dioxane is extracted 0.15ml (2.8mmol) 30% aqueous hydrogen peroxide solution with syringe, is added dropwise to system, white precipitate appears in vigorous stirring, reaction 3h.Sedimentation and filtration obtains white solid with 10ml dioxane, 2 * 10ml water and 10ml washing with acetone respectively with the white precipitate that obtains.
1H?NMR(CDCl
3)：7.558-7.768(10H)，7.194-7.544(12H)，7.120-7.193(2H)，7.036-7.118(2H)，5.983-6.080(2H)。
Add 333.3mg (1.5mmol) thienyl trifluoromethyl methyl ethyl diketone (TTA) in the two neck bottles and be dissolved in 15ml ethanol, drip 0.75ml 2M aqueous sodium hydroxide solution, be heated to 60 ℃, backflow 1h; Take by weighing 183.2mg (0.5mmol) six hydration europium chloride (EuCl
36H
2O) be dissolved in the 0.5ml water, drop in the system, 70 ℃ of following backflow 1h; With 290mg (0.5mmol) 2,2 '-diphenylphosphine oxygen base phenylate (DPEphos Oxide) is dissolved in 15ml ethanol, drops in the system, white precipitate occurs, and back flow reaction is spent the night.Sedimentation and filtration obtains white micro mist look solid with 2 * 10ml water, 2 * 10ml washing with alcohol respectively.
Add 343.3mg (1.5mmol) phenylbenzene methyl ethyl diketone (DBM) in the two neck bottles and be dissolved in the 15ml ethanol, drip 0.75ml 2M aqueous sodium hydroxide solution, be heated to 60 ℃, backflow 1h; Take by weighing 183.2mg (0.5mmol) six hydration europium chlorides and be dissolved in the 0.5ml water, drop in the system, 70 ℃ of following backflow 1h; With sedimentation and filtration, be dissolved in the 10ml tetrahydrofuran (THF), with 290mg (0.5mmol) 2,2 '-diphenylphosphine oxygen base phenylate is dissolved in 15ml ethanol, drop in the system, reaction is spent the night, and system is with methylene dichloride and water extraction separatory, after dichloromethane solution was spin-dried for, product obtained faint yellow solid with recrystallizing methanol.
At N
2Protection under-20 ℃, is got 2.4mmol n-BuLi and is dissolved in the 10ml anhydrous diethyl ether, stirs 30min; Get 0.28ml 1-bromonaphthalene and drop in the system, rise to 10 ℃ naturally, reaction is spent the night; After white precipitate appears in system, stop to stir and being cooled to-10 ℃, with the washing precipitation of 3 * 50ml anhydrous n-hexane; Drip 1.625ml n-BuLi and 0.42ml tetramethyl-Edamine, backflow is spent the night, and system becomes yellow suspension liquid; System temperature is reduced to 0 ℃ with the dissolving of 10ml tetrahydrofuran (THF), and system temperature is reduced to-78 ℃ and stirred 20min then, drips the 0.94ml diphenyl phosphine chloride, rises to room temperature naturally, and reaction is spent the night, and obtains taupe brown solution.The solution washing and drying is spin-dried for, and with the dissolving of 5ml benzene, adding 50ml methyl alcohol to separating out precipitation, system is left standstill 12h under-4 ℃, the yellow mercury oxide of separating out is filtered, and with methanol wash, the dry product that gets.
1H?NMR(CDCl
3)：8.128-8.059(2H)，7.753-7.664(2H)，7.524-7.389(14H)，7.373-7.292(8H)。
Get the two diphenylphosphine naphthalenes of 200mg in the 50ml flask, add 10ml 1,4-dioxane stirring and dissolving.Drip 0.6ml 30% aqueous hydrogen peroxide solution, stir 2h, solution becomes light green from yellow.System adds methylene chloride and the water extraction, and oil reservoir separates and removes residual dioxane with washing, and the oil reservoir drying is spin-dried for and obtains product, is white solid.Productive rate 98%.
1H?NMR(CDCl
3)：8.128-8.059(2H)，7.753-7.664(2H)，7.524-7.389(14H)，7.373-7.292(8H)。
Embodiment 7, rare earth compounding Eu (TTA)
3(Naphos Oxide's) is synthetic
Add 333.3mg (1.5mmol) thienyl trifluoromethyl methyl ethyl diketone in the two neck bottles and be dissolved in the 15ml ethanol, drip 0.75ml 2M aqueous sodium hydroxide solution, be heated to 60 ℃, backflow 1h; Take by weighing 183.2mg (0.5mmol) six hydration europium chlorides and be dissolved in the 0.5ml water, drop in the system, 70 ℃ of following backflow 1h; 327.3mg (0.5mmol) Naphos Oxide is dissolved in 15ml ethanol, drops in the system, white precipitate occurs, back flow reaction is spent the night.Sedimentation and filtration obtains white little yellow solid with 2 * 10ml water, 2 * 10ml washing with alcohol respectively.
1H?NMR(CDCl
3)：8.059-7.989(2H)，7.779-7.638(2H)，7.547-7.374(14H)，7.370-7.296(8H)。
Embodiment 8, rare earth compounding Eu (DBM)
3(Naphos Oxide's) is synthetic
Add 343.3mg (1.5mmol) phenylbenzene methyl ethyl diketone (DBM) in the two neck bottles and be dissolved in the 15ml ethanol, drip 0.75ml 2M aqueous sodium hydroxide solution, be heated to 60 ℃, backflow 1h; Take by weighing 183.2mg (0.5mmol) six hydration europium chlorides and be dissolved in the 0.5ml water, drop in the system, 70 ℃ of following backflow 1h; With sedimentation and filtration, be dissolved in the 10ml tetrahydrofuran (THF), 327.3mg (0.5mmol) Naphos Oxide is dissolved in 15ml ethanol, drop in the system, reaction is spent the night, and system is with methylene dichloride and water extraction separatory, after dichloromethane solution was spin-dried for, product obtained faint yellow solid with recrystallizing methanol.
The preparation of embodiment 9, electroluminescent device
One with rare earth compounding Eu (TTA)
3(DPEphos Oxide) and 4,4 '-N, the adulterate body of N '-carbazyl biphenyl (4,4 '-N, N '-carbazyl biphenyl (CBP)) is as the preparation of the electroluminescent device of luminescent layer.Luminescent layer is rare earth compounding Eu (TTA)
3(DPEphos Oxide) and 4,4 '-N, the dopant material of N '-carbazyl biphenyl, thickness are 30nm.It is the hole transmission layer (4,4 '-N, N '-naphthyl phenyl amine-biphenyl NPB) of 40nm that one layer thickness is arranged between luminescent layer and anode (tin indium oxide ITO).The film thickness of electric transmission/hole blocking layer is 30nm.Electron transfer layer is between electric transmission/hole blocking layer and negative electrode, and material therefor is 8-hydroxyquinoline aluminum (Alq
3), film thickness is 30nm.All material all adopts the vacuum thermal evaporation technology to film.The structure of device is: ITO/NPB (40nm)/Eu title complex: 4,4 '-N, N '-carbazyl biphenyl (CBP) (30nm)/BCP (30nm)/Alq (30nm)/LiF (5nm)/Al (100nm).
Claims (8)
1, a kind of aromatic base replacement diphosphine dioxide huge legendary turtle is closed rare earth compounding, it is characterized in that with the rare earth ion being central ion, is obtained through complex reaction by two kinds of parts, and its basic structure is as follows:
Wherein, Ar
1, Ar
2And Ar
3Be respectively the group that contains heteroatomic aromatic hydrocarbons, aromatic hydrocarbons or alkylaromatic hydrocarbon, and contain the derivative of alkyl, haloalkyl, halogenated aryl, halogen or alkylaromatic hydrocarbon group;
R
1, R
2And R
3Be respectively the group that contains alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon;
RE is a rare earth ion.
2, title complex according to claim 1 is characterized in that a kind of for following structure:
(1) central ion is three rank europium ions, and first part is a thienyl trifluoromethyl methyl ethyl diketone, and second part is 2,2 '-diphenylphosphine oxygen base phenylate, and its structural formula is (VI);
(2) central ion is three rank europium ions, and first part is the phenylbenzene methyl ethyl diketone, and second part is 2,2 '-diphenylphosphine oxygen base phenylate, and its structural formula is (VII);
(3) central ion is three rank europium ions, and first part is a thienyl trifluoromethyl methyl ethyl diketone, and second part is 1,8-diphenylphosphine oxygen base naphthalene, and its structural formula is (VIII);
(4) central ion is three rank europium ions, and first part is the phenylbenzene methyl ethyl diketone, and second part is 1,8-diphenylphosphine oxygen base naphthalene, and its structural formula is (IX);
3, a kind of synthetic method of title complex as claimed in claim 1 or 2 is characterized in that with alcohol as solvent, makes rare earth ion and following first, second part generation complex reaction form title complex under reflux temperature, and concrete operations are as follows:
Get three normal first parts and be dissolved in the ethanol, 50～70 ℃ of aqueous sodium hydroxide solution neutralizations that drip equivalent down, the reaction times is 15～60 minutes;
Get the inorganic salt of rare earth of monovalent or rare earth organic compounds is water-soluble or organic solvent and dropping in the system, temperature is controlled at 70～80 ℃, reacts 30～60 minutes;
Second part of getting monovalent is dissolved in ethanol and drops in the system, and temperature maintenance is at 70～80 ℃, and the reaction times is 2～4 hours;
In the above-mentioned synthesis step, first part of employing is the beta-diketon class, and the structure of this compound is as follows:
Wherein, R
1, R
2And R
3Be respectively the group that contains alkyl, haloalkyl, aryl, halogenated aryl, halogenated alkane or alkylaromatic hydrocarbon.
4,, it is characterized in that the synthesis step of described second part aromatic base replacement diphosphine dioxide is as follows according to the synthetic method of the described title complex of claim 3:
Work as Ar
2And Ar
3During for phenyl, use diphenyl phosphine chloride as phosphonate reagent;
Get monovalent Ar
1Bromide is dissolved in anhydrous diethyl ether or tetrahydrofuran (THF), drips two normal n-Butyl Lithiums down at-78～0 ℃, reacts 1～2 hour, at room temperature reacts then 0.5～1 hour;
System is reduced to-78～0 ℃, slowly drip diphenyl phosphine chloride ether or tetrahydrofuran solution, reacted 2-3 hour; At room temperature reacted then 8～24 hours, and obtained aromatic base and replace two phosphine things;
Be dissolved in top two phosphine things in the dioxane solvent and drip 1.5 normal hydrogen peroxide oxidations, at room temperature reacted 2～4 hours, promptly obtain aromatic base and replace diphosphine dioxide.
5,, it is characterized in that the synthesis step of described second part aromatic base replacement diphosphine dioxide is as follows according to the synthetic method of the described title complex of claim 3:
Work as Ar
2And Ar
3During for the distinct fragrance group, using phosphorus trichloride as phosphonate reagent, is solvent with anhydrous diethyl ether or tetrahydrofuran (THF), is progressively adding Ar under-78～0 ℃ in 3.5 normal phosphorus trichlorides
2And Ar
3Lithium for thing, keep phosphorus trichloride excessive; The phosphonate reagent system that obtains is dropped to the Ar of monovalent
1React in the ether of lithiumation thing or the tetrahydrofuran solution, the phosphine thing that reaction is obtained promptly obtains aromatic base and replaces diphosphine dioxide with 1.5 normal hydrogen peroxide oxidations.
6, a kind of title complex according to claim 1 is as the application of electroluminescent material in the ruddiness device.
7, the application of title complex according to claim 6, it is characterized in that at first making conductive layer, vacuum evaporation hole mobile material on conductive layer then, the adulterated luminescent layer of the described rare earth compounding of evaporation again, evaporation electric transmission hole barrier materials on it, follow the evaporation electron transfer layer, last evaporation second layer conductive layer.
8, the application of title complex according to claim 7 is characterized in that described doping luminescent layer is described rare earth compounding and 4,4 '-N, the adulterate body of N '-carbazyl biphenyl.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011013520A1 (en) * | 2009-07-29 | 2011-02-03 | 国立大学法人奈良先端科学技術大学院大学 | Rare-earth complex and uses thereof |
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| CN103936779A (en) * | 2014-05-12 | 2014-07-23 | 黑龙江大学 | Triarylamine group modified diphenyl ether bidentate aromatic phosphine oxide europium complex as well as synthetic method and application thereof |
| CN103936775A (en) * | 2014-05-12 | 2014-07-23 | 黑龙江大学 | Dibenzothiophene-based bidentate aromatic phosphine-oxygen-europium complex modified by carbazole groups as well as synthetic method and application thereof |
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| CN103980303A (en) * | 2014-05-12 | 2014-08-13 | 黑龙江大学 | Carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, synthesis method and applications thereof |
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| WO2011013520A1 (en) * | 2009-07-29 | 2011-02-03 | 国立大学法人奈良先端科学技術大学院大学 | Rare-earth complex and uses thereof |
| US20120140439A1 (en) * | 2009-07-29 | 2012-06-07 | National University Corporation NARA Institute of Science and Technology | Rare-earth complex and uses thereof |
| JP5737719B2 (en) * | 2009-07-29 | 2015-06-17 | 国立大学法人 奈良先端科学技術大学院大学 | Rare earth complexes and their use |
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| CN102503980A (en) * | 2011-11-01 | 2012-06-20 | 黑龙江大学 | Photoelectric functional aromatic phosphine oxide compound, and preparation method and application thereof |
| CN102807592A (en) * | 2012-08-23 | 2012-12-05 | 四川省新材料研究中心 | Series cyclic rare-earth complexes for inducing movement of double emission spectra by aggregation and preparation method thereof |
| CN102807592B (en) * | 2012-08-23 | 2015-02-04 | 四川省新材料研究中心 | Series cyclic rare-earth complexes for inducing movement of double emission spectra by aggregation and preparation method thereof |
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| CN103936777A (en) * | 2014-05-12 | 2014-07-23 | 黑龙江大学 | Diethylfluorenyl-modified double-tooth aromatic phosphine oxygen europium complex, and synthesis method application thereof |
| CN103980302B (en) * | 2014-05-12 | 2016-03-30 | 黑龙江大学 | A kind of with the application of the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification |
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| CN103936777B (en) * | 2014-05-12 | 2016-03-30 | 黑龙江大学 | The application of the bidentate aromatic phosphines oxygen europium complex modified with diethyl fluorene group |
| WO2020013087A1 (en) * | 2018-07-10 | 2020-01-16 | 国立大学法人北海道大学 | Rare-earth complex, light-emitting material, light-emitting object, light-emitting device, interlayer for laminated glass, laminated glass, windshield for vehicle, wavelength conversion material, and security material |
| JPWO2020013087A1 (en) * | 2018-07-10 | 2021-08-19 | 国立大学法人北海道大学 | Rare earth complexes, light-emitting materials, light-emitting bodies, light-emitting devices, interlayer films for laminated glass, laminated glass, windshields for vehicles, wavelength conversion materials and security materials |
| JP7317376B2 (en) | 2018-07-10 | 2023-07-31 | 国立大学法人北海道大学 | Rare earth complexes, luminescent materials, luminescent bodies, luminescent devices, interlayer films for laminated glass, laminated glass, windshields for vehicles, wavelength conversion materials and security materials |
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