CN103936776A - Triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide europium complex as well as synthetic method and application thereof - Google Patents
Triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide europium complex as well as synthetic method and application thereof Download PDFInfo
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 108
- -1 Triarylamine group modified dibenzofuran Chemical class 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- LZYBCYGUKVUMBA-UHFFFAOYSA-N [Eu].[PH3]=O Chemical compound [Eu].[PH3]=O LZYBCYGUKVUMBA-UHFFFAOYSA-N 0.000 title abstract 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 136
- 125000005259 triarylamine group Chemical group 0.000 claims description 133
- 150000003003 phosphines Chemical class 0.000 claims description 102
- FYZGFASBNJXJGO-UHFFFAOYSA-N oxoeuropium Chemical compound [Eu]=O FYZGFASBNJXJGO-UHFFFAOYSA-N 0.000 claims description 87
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000004448 titration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000036571 hydration Effects 0.000 claims description 10
- 238000006703 hydration reaction Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- LCOMFVDNVLHUEK-UHFFFAOYSA-N C(C)C(=O)C(=O)C.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C)C(=O)C(=O)C.C1(=CC=CC=C1)C1=CC=CC=C1 LCOMFVDNVLHUEK-UHFFFAOYSA-N 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 256
- 238000010521 absorption reaction Methods 0.000 description 34
- 238000001228 spectrum Methods 0.000 description 32
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 19
- 238000000862 absorption spectrum Methods 0.000 description 16
- 230000005855 radiation Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 0 CC(C(C1CC(C2)C2CC1)C(C*C1C2C1)C(C1=C3C1)=C2C(C1)C3=C(CC(*)(C2=CC=CCC2)c2ccccc2)C=C1C1=CC(C2)[C@@]2(*(C2CC=CCC2)*2=CC(CCCC3)C3=CCC2)C2C1C2)*1ccccc1 Chemical compound CC(C(C1CC(C2)C2CC1)C(C*C1C2C1)C(C1=C3C1)=C2C(C1)C3=C(CC(*)(C2=CC=CCC2)c2ccccc2)C=C1C1=CC(C2)[C@@]2(*(C2CC=CCC2)*2=CC(CCCC3)C3=CCC2)C2C1C2)*1ccccc1 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical compound P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide europium complex as well as a synthetic method and application thereof, relates to a europium complex as well as a synthetic method and application thereof and aims to solve the problems that neutral ligands of existing rare earth complexes have poor hole injection and transport capacities and poor heat stability and the luminous efficiency is low when the rare earth complexes are applied to electroluminescent devices. The structure of the complex is shown in the specification. A preparation method is characterized by preparing the triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide europium complex by using a beta-diketone/absolute ethyl alcohol mixed solution, a sodium hydroxide water solution, a europium chloride water solution and a triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide ligand/dichloromethane solution as the raw materials. The triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide europium complex as a luminous layer material is applied to the electroluminescent devices. The triarylamine group modified dibenzofuran bidentate aromatic phosphine oxide europium complex can be obtained.
Description
Technical field
The present invention relates to a kind of europium complex and synthetic method thereof and application.
Background technology
In recent years, people show keen interest to the research of rare earth compounding luminescent properties, its reason is that rare earth compounding luminous has high luminous quantum efficiency and high color purity etc. (peak width at half height is only 10nm left and right) feature, is to obtain the preferred material that high quality flat shows.Because rare earth ion self luminous efficiency is low, the high-luminous-efficiency of rare earth compounding derives from the absorption of organic ligand to energy and the part transmission ofenergy to central ion, the organic ligand of the high absorption coefficient that therefore, searching is mated with rare earth ion energy level is still the direction that people make great efforts.Europium beta-diketon class title complex can send at 613nm place the ruddiness that monochromaticity is fabulous, is the more class red emission material of current electroluminescent area research.Research shows: in europium beta-diketone complex, introduce thermostability, luminous efficiency and carrier transport that some neutral ligand can improve title complex, thereby improve the luminous efficiency of electroluminescent device.Therefore, design synthesizing new neutral ligand plays a part very important to the application and development of rare-earth complexes luminous material.
Existing rare earth compounding is applied to and in electroluminescent device, has luminous intensity and inefficient shortcoming.From structure, select bidentate phosphine oxygen not only can improve the stability of rare earth compounding structure as neutral ligand, can also also play very important effect to title complex carrier transport.The electroluminescent material efficiency of rare earth compounding is generally on the low side, and this is because the carrier transport ability of title complex is poor.
Summary of the invention
The neutral ligand that the object of the invention is to solve existing rare earth compounding exist to hole inject and transmittability a little less than, poor heat stability, rare earth compounding is applied to and in electroluminescent device, has the problem that luminous efficiency is low, and a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex and synthetic method and application of modifying with triarylamine group is provided.
Neutral ligand and beta-diketonate ligand complexing europium ion that a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is formed by the derivative of dibenzofuran group bidentate aromatic phosphines oxygen form, and structure is:
wherein, described Ar
1during for H, Ar
2for
or
or Ar
1for
or
and Ar
1with Ar
2structural formula identical;
Described R
1during for phenyl, R
2for phenyl;
Described R
1for CF
3time, R
2for α-thienyl.
A synthetic method for the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is to carry out according to the following steps:
One, beta-diketon is dissolved in dehydrated alcohol, obtains beta-diketon/dehydrated alcohol mixing solutions;
The amount of substance of the beta-diketon described in step 1 and the volume ratio of dehydrated alcohol are (0.1mmol～0.2mmol): 1mL;
Two, six hydration europium chlorides are dissolved in distilled water, obtain the europium chloride aqueous solution;
Six amount of substances of hydration europium chloride described in step 2 and the volume ratio of distilled water are (0.5mmol～1.5mmol): 1mL;
Three, the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The amount of substance of dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 and the volume ratio of methylene dichloride are as 1mmol:(30mL～40mL);
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, under rate of titration is the condition of 5/min～10 droplet/min, the aqueous sodium hydroxide solution of 12mol/L～15mol/L is added drop-wise in container, be the 1h～3h that refluxes under the condition of 60 DEG C～70 DEG C in temperature, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min～10 droplet/min, be the 1h～3h that refluxes under the condition of 60 DEG C～70 DEG C in temperature, the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution that to modify with triarylamine group with the rate of titration of 5/min～10 droplet/min is again added drop-wise in container, be back flow reaction 12h～18h under the condition of 60 DEG C～70 DEG C in temperature, re-using Rotary Evaporators steams alcohol solvent, obtain powdery precipitate,
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and beta-diketon/dehydrated alcohol mixing solutions is (0.05～0.1): 1;
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and the europium chloride aqueous solution is (1～1.5): 1;
In the amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with triarylamine group described in step 4 and beta-diketon/dehydrated alcohol mixing solutions, the amount of substance ratio of beta-diketon is as 1:3;
Five, powdery precipitate is used to distilled water filtering and washing 2 times～3 times, re-use dehydrated alcohol filtering and washing 2 times～3 times, be dry 6h～8h under the condition of 60 DEG C～70 DEG C in temperature again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group;
The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPOTPA, DBFDPODPNA, DBFDPOTPA2 or DBFDPODPNA2; Described DBFDPOTPA structural formula is
described DBFDPODPNA structural formula is
described DBFDPOTPA2 structural formula is
described DBFDPODPNA2 structural formula is
A kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying using triarylamine group is applied in electroluminescent device as luminescent layer material.
Advantage of the present invention: one, with triarylamine group, dibenzofuran group bidentate aromatic phosphines oxygen is carried out to functional modification, the cavity transmission group of introducing can improve hole and inject and transmittability, has also improved the thermostability of title complex simultaneously;
Two, the present invention is when for electroluminescent device, and luminous efficiency is high, and luminescent device purity of color is high.
The present invention can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
Brief description of the drawings
Fig. 1 is the synthetic Eu (DBM) of test one
3(DBFDPOTPA) Ultraluminescence spectrum; In Fig. 1-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 2 is the synthetic Eu (TTA) of test three
3(DBFDPOTPA) Ultraluminescence spectrum; In Fig. 2-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 3 is the Eu (DBM) that test pentahapto becomes
3(DBFDPODPNA) Ultraluminescence spectrum; In Fig. 3-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 4 is the synthetic Eu (TTA) of test seven
3(DBFDPODPNA) Ultraluminescence spectrum; In Fig. 4-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 5 is the synthetic Eu (DBM) of test nine
3(DBFDPOTPA2) Ultraluminescence spectrum; In Fig. 5-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 6 is the synthetic Eu (TTA) of test 11
3(DBFDPOTPA2) Ultraluminescence spectrum; In Fig. 6-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 7 is the synthetic Eu (DBM) of test 13
3(DBFDPODPNA2) Ultraluminescence spectrum; In Fig. 7-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 8 is the Eu (TTA) that test ten pentahaptos become
3(DBFDPODPNA2) Ultraluminescence spectrum; In Fig. 8-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum;
Fig. 9 is the synthetic Eu (DBM) of test one
3(DBFDPOTPA) infrared spectrogram;
Figure 10 is the synthetic Eu (TTA) of test three
3(DBFDPOTPA) infrared spectrogram;
Figure 11 is the Eu (DBM) that test pentahapto becomes
3(DBFDPODPNA) infrared spectrogram;
Figure 12 is the synthetic Eu (TTA) of test seven
3(DBFDPODPNA) infrared spectrogram;
Figure 13 is the synthetic Eu (DBM) of test nine
3(DBFDPOTPA2) infrared spectrogram;
Figure 14 is the synthetic Eu (TTA) of test 11
3(DBFDPOTPA2) infrared spectrogram;
Figure 15 is the synthetic Eu (DBM) of test 13
3(DBFDPODPNA2) infrared spectrogram;
Figure 16 is the Eu (TTA) that test ten pentahaptos become
3(DBFDPODPNA2) infrared spectrogram;
Figure 17 is the synthetic Eu (DBM) of test two use-testings one
3(DBFDPOTPA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 17-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 18 is the synthetic Eu (TTA) of test four use-testings three
3(DBFDPOTPA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 18-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 19 is the Eu (DBM) that test six use-testing pentahaptos become
3(DBFDPODPNA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 19-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 20 is the synthetic Eu (TTA) of test eight use-testings seven
3(DBFDPODPNA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 20-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 21 is the synthetic Eu (DBM) of test ten use-testings nine
3(DBFDPOTPA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 21-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 22 is the synthetic Eu (TTA) of test 12 use-testings 11
3(DBFDPOTPA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 22-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 23 is the synthetic Eu (DBM) of test 14 use-testings 13
3(DBFDPODPNA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 23-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 24 is the Eu (TTA) that test 16 use-testing ten pentahaptos become
3(DBFDPODPNA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 24-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 25 is the synthetic Eu (DBM) of test two use-testings one
3(DBFDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 26 is the synthetic Eu (TTA) of test four use-testings three
3(DBFDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 27 is the Eu (DBM) that test six use-testing pentahaptos become
3(DBFDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 28 is the synthetic Eu (TTA) of test eight use-testings seven
3(DBFDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 29 is the synthetic Eu (DBM) of test ten use-testings nine
3(DBFDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 30 is the synthetic Eu (TTA) of test 12 use-testings 11
3(DBFDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 31 is the synthetic Eu (DBM) of test 14 use-testings 13
3(DBFDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device;
Figure 32 is the Eu (TTA) that test 16 use-testing ten pentahaptos become
3(DBFDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.
Embodiment
Embodiment one: present embodiment is that neutral ligand and the beta-diketonate ligand complexing europium ion that a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is formed by the derivative of dibenzofuran group bidentate aromatic phosphines oxygen forms, and structure is:
wherein, described Ar
1during for H, Ar
2for
or
or Ar
1for
or
and Ar
1with Ar
2structural formula identical;
Described R
1during for phenyl, R
2for phenyl;
Described R
1for CF
3time, R
2for α-thienyl.
The advantage of present embodiment: one, with triarylamine group, dibenzofuran group bidentate aromatic phosphines oxygen is carried out to functional modification, the cavity transmission group of introducing can improve hole and inject and transmittability, has also improved the thermostability of title complex simultaneously;
Two, present embodiment is when for electroluminescent device, and luminous efficiency is high, and luminescent device purity of color is high.
Present embodiment can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
Embodiment two: present embodiment is a kind of synthetic method of the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group, is to carry out according to the following steps:
One, beta-diketon is dissolved in dehydrated alcohol, obtains beta-diketon/dehydrated alcohol mixing solutions;
The amount of substance of the beta-diketon described in step 1 and the volume ratio of dehydrated alcohol are (0.1mmol～0.2mmol): 1mL;
Two, six hydration europium chlorides are dissolved in distilled water, obtain the europium chloride aqueous solution;
Six amount of substances of hydration europium chloride described in step 2 and the volume ratio of distilled water are (0.5mmol～1.5mmol): 1mL;
Three, the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The amount of substance of dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 and the volume ratio of methylene dichloride are as 1mmol:(30mL～40mL);
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, under rate of titration is the condition of 5/min～10 droplet/min, the aqueous sodium hydroxide solution of 12mol/L～15mol/L is added drop-wise in container, be the 1h～3h that refluxes under the condition of 60 DEG C～70 DEG C in temperature, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min～10 droplet/min, be the 1h～3h that refluxes under the condition of 60 DEG C～70 DEG C in temperature, the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution that to modify with triarylamine group with the rate of titration of 5/min～10 droplet/min is again added drop-wise in container, be back flow reaction 12h～18h under the condition of 60 DEG C～70 DEG C in temperature, re-using Rotary Evaporators steams alcohol solvent, obtain powdery precipitate,
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and beta-diketon/dehydrated alcohol mixing solutions is (0.05～0.1): 1;
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and the europium chloride aqueous solution is (1～1.5): 1;
In the amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with triarylamine group described in step 4 and beta-diketon/dehydrated alcohol mixing solutions, the amount of substance ratio of beta-diketon is as 1:3;
Five, powdery precipitate is used to distilled water filtering and washing 2 times～3 times, re-use dehydrated alcohol filtering and washing 2 times～3 times, be dry 6h～8h under the condition of 60 DEG C～70 DEG C in temperature again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group;
The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPOTPA, DBFDPODPNA, DBFDPOTPA2 or DBFDPODPNA2; Described DBFDPOTPA structural formula is
described DBFDPODPNA structural formula is
described DBFDPOTPA2 structural formula is
described DBFDPODPNA2 structural formula is
The advantage of present embodiment: one, with triarylamine group, dibenzofuran group bidentate aromatic phosphines oxygen is carried out to functional modification, the cavity transmission group of introducing can improve hole and inject and transmittability, has also improved the thermostability of title complex simultaneously;
Two, present embodiment is when for electroluminescent device, and luminous efficiency is high, and luminescent device purity of color is high.
Present embodiment can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
Embodiment three: present embodiment and embodiment two differences are: the beta-diketon described in step 1 is phenylbenzene methyl ethyl diketone or thienyl trifluoromethyl methyl ethyl diketone.Other steps are identical with embodiment two.
Embodiment four: one of present embodiment and embodiment two or three difference is: the amount of substance of the beta-diketon described in step 1 and the volume ratio of dehydrated alcohol are (0.15mmol～0.2mmol): 1mL.Other steps are identical with embodiment two or three.
Embodiment five: one of present embodiment and embodiment two to four difference is: six amount of substances of hydration europium chloride described in step 2 and the volume ratio of distilled water are (0.8mmol～1.5mmol): 1mL.Other steps are identical with embodiment two to four.
Embodiment six: one of present embodiment and embodiment two to five difference is: the volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and beta-diketon/dehydrated alcohol mixing solutions is (0.08～0.1): 1.Other steps are identical with embodiment two to five.
Embodiment seven: one of present embodiment and embodiment two to six difference is: the volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and the europium chloride aqueous solution is (1.2～1.5): 1.Other steps are identical with embodiment two to six.
Embodiment eight: one of present embodiment and embodiment two to seven difference is: the amount of substance of dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 and the volume ratio of methylene dichloride are as 1mmol:(30mL～35mL).Other steps are identical with embodiment two to seven.
Embodiment nine: one of present embodiment and embodiment two to eight difference is: in step 5, powdery precipitate is used to distilled water filtering and washing 2 times～3 times, re-use dehydrated alcohol filtering and washing 2 times～3 times, be dry 7h～8h under the condition of 65 DEG C～70 DEG C in temperature again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.Other steps are identical with embodiment two to eight.
Embodiment ten: present embodiment is that a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying using triarylamine group is applied in electroluminescent device as luminescent layer material.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of Eu (DBM)
3(DBFDPOTPA) synthetic method of the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is to carry out according to the following steps:
One, beta-diketon is dissolved in dehydrated alcohol, obtains beta-diketon/dehydrated alcohol mixing solutions;
The amount of substance of the beta-diketon described in step 1 and the volume ratio of dehydrated alcohol are 0.1mmol:1mL;
Two, six hydration europium chlorides are dissolved in distilled water, obtain the europium chloride aqueous solution;
Six amount of substances of hydration europium chloride described in step 2 and the volume ratio of distilled water are 1mmol:1mL;
Three, the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The amount of substance of dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 and the volume ratio of methylene dichloride are as 1mmol:30mL;
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, under rate of titration is the condition of 5/min, the aqueous sodium hydroxide solution of 12mol/L is added drop-wise in container, be the 1h that refluxes under the condition of 70 DEG C in temperature, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min, be the 1h that refluxes under the condition of 70 DEG C in temperature, with the rate of titration of 5/min, dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group is added drop-wise in container again, be back flow reaction 12h under the condition of 70 DEG C in temperature, re-using Rotary Evaporators steams alcohol solvent, obtain powdery precipitate,
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L described in step 4 and beta-diketon/dehydrated alcohol mixing solutions is 0.05:1;
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L described in step 4 and the europium chloride aqueous solution is 1:1;
In the amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with triarylamine group described in step 4 and beta-diketon/dehydrated alcohol mixing solutions, the amount of substance ratio of beta-diketon is as 1:3;
Five, powdery precipitate is used to distilled water filtering and washing 3 times, re-use dehydrated alcohol filtering and washing 3 times, then be dry 8h under the condition of 70 DEG C in temperature, obtain structural formula and be
the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group
3(DBFDPOTPA).
Beta-diketon described in step 1 is phenylbenzene methyl ethyl diketone;
The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPOTPA, and described DBFDPOTPA structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPOTPA according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of test one is as follows:
Use elemental analyser to testing a synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group
3(DBFDPOTPA) carry out ultimate analysis test, obtain data as follows:
Eu (DBM)
3(DBFDPOTPA) theoretical value: C is 72.79; H is 4.44; Eu is 9.30; N is 0.86; O is 8.81; And actual measured value: C is 72.85; H is 4.29; Eu is 9.41; N is 0.74; O is 8.77.
Use ultraviolet-visible pectrophotometer and FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph to testing the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPOTPA) test, as shown in Figure 1, Fig. 1 is the synthetic Eu (DBM) of test one
3(DBFDPOTPA) Ultraluminescence spectrum; In Fig. 1-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 1, there is the characteristic emission peak of europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing a synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group
3(DBFDPOTPA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in Figure 9, Fig. 9 is the synthetic Eu (DBM) of test one
3(DBFDPOTPA) infrared spectrogram.As can be seen from Figure 9, at 3059cm
-1, 1971cm
-1, 1607cm
-1and 1567cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1536cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in DBM, at 1519cm
-1and 1466cm
-1having absorption peak, is the stretching vibration peak of C-P, at 1415cm
-1, 1353cm
-1, 1301cm
-1, 1245cm
-1, 1229cm
-1and 1164cm
-1having absorption peak, is the stretching vibration peak of P=O.
Test two: coat the hole transmission layer that a layer thickness is 60nm between tin indium oxide ITO is as anode and luminescent layer, Ca is electron injecting layer, electrode materials is aluminium, and the electron injecting layer of electrode materials adopts vacuum evaporation technology film, and hole transmission layer and luminescent layer adopt spin coating technique film.The structure of device is: ITO/PEDTO/PSS (60nm)/PVK:PBD: the dibenzofuran group bidentate aromatic phosphines oxygen europium complex (65:30:5 modifying with triarylamine group; 60nm)/Ca (25nm)/Al (100nm);
Luminescent layer described in test two is the synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group of test one
3(DBFDPOTPA), the dopant material of PVK and PBD; In luminescent layer described in test two, test a synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group
3(DBFDPOTPA) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts; The thickness of the luminescent layer described in test two is 60nm; The electron injecting layer of the electrode materials described in test two adopts vacuum evaporation technology film, and hole transmission layer and luminescent layer adopt spin coating technique film;
PEDTO/PSS described in test two is poly-3,4-ethylene dioxythiophene/poly styrene sulfonate;
PVK described in test two is Polyvinyl carbazole;
PBD described in test two is 2-(4'-trimethylphenylmethane base)-5-(4'-xenyl)-1,3,4-oxadiazoles.
Use PR650 and Keithley2400 instrument to test a synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group
3(DBFDPOTPA) electroluminescent device of making as luminescent layer material is tested, and as shown in figure 17, Figure 17 is the synthetic Eu (DBM) of test two use-testings one
3(DBFDPOTPA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 17-and-be current density voltage curve ,-■-be brightness-voltage curve.As shown in Figure 17, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 25 is the synthetic Eu (DBM) of test two use-testings one
3(DBFDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device, as can be seen from Figure 25, the characteristic emission peak that 612nm place is Eu.
Test three: this test with test one difference is: the beta-diketon described in step 1 is thienyl trifluoromethyl methyl ethyl diketone.Other step and parameter are identical with test one.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that test three is synthetic
3(DBFDPOTPA) structural formula is
the reaction formula of this test is as follows:
Use elemental analyser to testing the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA)
3(DBFDPOTPA) theoretical value: C is 57.57; H is 3.16; Eu is 9.34; N is 0.86; O is 8.85; S is 5.91; And actual measured value: C is 57.63; H is 3.29; Eu is 9.16; N is 0.84; O is 8.68; S is 5.76.
Use ultraviolet-visible pectrophotometer and FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph to testing the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA) test, as shown in Figure 2, Fig. 2 is the synthetic Eu (TTA) of test three
3(DBFDPOTPA) Ultraluminescence spectrum; In Fig. 2-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 2, there is the characteristic emission peak of europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in figure 10, Figure 10 is the synthetic Eu (TTA) of test three
3(DBFDPOTPA) infrared spectrogram.As can be seen from Figure 10, at 3054cm
-1, 1610cm
-1and 1567cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1537cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1521cm
-1, 1502cm
-1and 1467cm
-1having absorption peak, is the stretching vibration peak of C-P, at 1415cm
-1, 1352cm
-1, 1303cm
-1, 1245cm
-1, 1230cm
-1and 1177cm
-1having absorption peak, is the stretching vibration peak of P=O.
Test four: this test with test two differences is: the described luminescent layer of this test is the synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group of test three
3(DBFDPOTPA), the dopant material of PVK and PBD; In described luminescent layer, test the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 and Keithley2400 instrument to test the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 18, Figure 18 is the synthetic Eu (TTA) of test four use-testings three
3(DBFDPOTPA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 18-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 18, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 26 is the synthetic Eu (TTA) of test four use-testings three
3(DBFDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 26, the characteristic emission peak that 612nm place is Eu.
Test five: this test with test one difference is: the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPODPNA; Described DBFDPODPNA structural formula is
other step and parameter are identical with test one.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that test pentahapto becomes
3(DBFDPODPNA) structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPODPNA according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of this test is as follows:
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that uses elemental analyser to become test pentahapto
3(DBFDPODPNA) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM)
3(DBFDPODPNA) theoretical value: C is 73.48; H is 4.43; Eu is 9.03; N is 0.83; O is 8.55; And actual observed value: C is 73.62; H is 4.36; Eu is 9.19; N is 0.78; O is 8.36.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that uses ultraviolet-visible pectrophotometer with FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph, test pentahapto to be become
3(DBFDPODPNA) test, as shown in Figure 3, Fig. 3 is the Eu (DBM) that test pentahapto becomes
3(DBFDPODPNA) Ultraluminescence spectrum; In Fig. 3-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 3, there is the characteristic emission peak of europium ion at 612nm place.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that uses Perkin-Elmer60000 infrared spectrometer to become test pentahapto
3(DBFDPODPNA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in figure 11, Figure 11 is the Eu (DBM) that test pentahapto becomes
3(DBFDPODPNA) infrared spectrogram.As can be seen from Figure 11, at 3056cm
-1and 1597cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1550cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in DBM, at 1519cm
-1, 1479cm
-1, 1459cm
-1and 1437cm
-1having absorption peak, is the stretching vibration peak of C-P, at 1416cm
-1, 1311cm
-1, 1221cm
-1, 1169cm
-1and 1132cm
-1having absorption peak, is the stretching vibration peak of P=O.
Test six: this test with test two differences is: the described luminescent layer of this test is the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that test pentahapto becomes
3(DBFDPODPNA), the dopant material of PVK and PBD; In described luminescent layer, test the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that pentahapto becomes
3(DBFDPODPNA) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 to roll into a ball with triarylamine the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying to what become with test test pentahapto with Keithley2400 instrument
3(DBFDPODPNA) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 19, Figure 19 is the Eu (DBM) that test six use-testing pentahaptos become
3(DBFDPODPNA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 19-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 19, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 27 is the Eu (DBM) that test six use-testing pentahaptos become
3(DBFDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 27, the characteristic emission peak that 612nm place is Eu.
Test seven: this test with test one difference is: the beta-diketon described in step 1 is thienyl trifluoromethyl methyl ethyl diketone; The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPODPNA; Described DBFDPODPNA structural formula is
other step and parameter are identical with test one.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that test seven is synthetic
3(DBFDPODPNA) structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPODPNA according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPODPNA) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA)
3(DBFDPODPNA) theoretical value: C is 58.71; H is 3.18; Eu is 9.06; N is 0.84; O is 8.58; S is 5.73; Observed value: C is 58.66; H is 3.27; Eu is 8.88; N is 0.96; O is 8.41; S is 5.50.
Use ultraviolet-visible pectrophotometer and FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph to testing the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPODPNA) test, as shown in Figure 4, Fig. 4 is the synthetic Eu (TTA) of test seven
3(DBFDPODPNA) Ultraluminescence spectrum; In Fig. 4-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 4, there is the characteristic emission peak of europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPODPNA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in figure 12, Figure 12 is the synthetic Eu (TTA) of test seven
3(DBFDPODPNA) infrared spectrogram.As can be seen from Figure 12, at 3066cm
-1, 1636cm
-1and 1612cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1535cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1518cm
-1, 1499cm
-1, 1475cm
-1and 1438cm
-1having absorption peak, is the stretching vibration peak of C-P, at 1414cm
-1, 1401cm
-1, 1357cm
-1, 1307cm
-1, 1179cm
-1and 1139cm
-1having absorption peak, is the stretching vibration peak of P=O.
Test eight: this test with test two differences is: the described luminescent layer of this test is the synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group of test seven
3(DBFDPODPNA), the dopant material of PVK and PBD; In described luminescent layer, test the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPODPNA) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 and Keithley2400 instrument to test the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPODPNA) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 20, Figure 20 is the synthetic Eu (TTA) of test eight use-testings seven
3(DBFDPODPNA) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 20-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 20, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 28 is the synthetic Eu (TTA) of test eight use-testings seven
3(DBFDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 28, the characteristic emission peak that 612nm place is Eu.
Test nine: this test with test one difference is: the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPOTPA2; Described DBFDPOTPA2 structural formula is
other step and parameter are identical with test one.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that test nine is synthetic
3(DBFDPOTPA2) structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPOTPA2 according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPOTPA2) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM)
3(DBFDPOTPA2) theoretical value: C is 74.87; H is 4.56; Eu is 8.10; N is 1.49; O is 7.67; And actual measured value: C is 74.78; H is 4.32; Eu is 8.05; N is 1.55; O is 7.78.
Use ultraviolet-visible pectrophotometer and FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph to testing the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPOTPA2) test, as shown in Figure 5, Fig. 5 is the synthetic Eu (DBM) of test nine
3(DBFDPOTPA2) Ultraluminescence spectrum; In Fig. 5-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 5, there is the characteristic emission peak of europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPOTPA2) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in figure 13, Figure 13 is the synthetic Eu (DBM) of test nine
3(DBFDPOTPA2) infrared spectrogram.As can be seen from Figure 13, at 3057cm
-1and 1622cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1532cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in DBM,, at 1485cm
-1and 1437cm
-1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm
-1, 1323cm
-1, 1288cm
-1, 1178cm
-1and 1131cm
-1there is absorption peak at place, is the stretching vibration peak of P=O.
Test ten: this test with test two differences is: the described luminescent layer of this test is the synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group of test nine
3(DBFDPOTPA2), the dopant material of PVK and PBD; In described luminescent layer, test the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPOTPA2) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 and Keithley2400 instrument to test the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPOTPA2) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 21, Figure 21 is the synthetic Eu (DBM) of test ten use-testings nine
3(DBFDPOTPA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 21-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 21, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 29 is the synthetic Eu (DBM) of test ten use-testings nine
3(DBFDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 29, the characteristic emission peak that 612nm place is Eu.
Test 11: this test with test one difference is: the beta-diketon described in step 1 is thienyl trifluoromethyl methyl ethyl diketone; The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPOTPA2; Described DBFDPOTPA2 structural formula is
.Other step and parameter are identical with test one.
Test the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA2) structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPOTPA2 according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA2) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA)
3(DBFDPOTPA2) theoretical value: C is 61.64; H is 3.45; Eu is 8.12; N is 1.50; O is 7.70; S is 5.14; And actual measured value: C is 61.54; H is 3.34; Eu is 8.02; N is 1.57; O is 7.59; S is 5.27.
Use ultraviolet-visible pectrophotometer and FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph to testing the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA2) test, as shown in Figure 6, Fig. 6 is the synthetic Eu (TTA) of test 11
3(DBFDPOTPA2) Ultraluminescence spectrum; In Fig. 6-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 6, there is the characteristic emission peak of europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA2) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in figure 14, Figure 14 is the synthetic Eu (TTA) of test 11
3(DBFDPOTPA2) infrared spectrogram.As can be seen from Figure 14, at 3056cm
-1and 1595cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1547cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1518cm
-1, 1478cm
-1, 1454cm-1 and 1437cm
-1there is absorption peak at place, is the stretching vibration peak of C-P, at 1394cm
-1, 1307cm
-1, 1178cm
-1, 1138cm-1 and 1102cm
-1there is absorption peak at place, is the stretching vibration peak of P=O.
Test 12: this test with test two differences is: the described luminescent layer of this test is the synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group of test 11
3(DBFDPOTPA2), the dopant material of PVK and PBD; In described luminescent layer, test the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA2) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 and Keithley2400 instrument to test the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group
3(DBFDPOTPA2) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 22, Figure 22 is the synthetic Eu (TTA) of test 12 use-testings 11
3(DBFDPOTPA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 22-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 22, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 30 is the synthetic Eu (TTA) of test 12 use-testings 11
3(DBFDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 30, the characteristic emission peak that 612nm place is Eu.
Test 13: this test with test one difference is: the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPODPNA2; Described DBFDPODPNA2 structural formula is
other step and parameter are identical with test one.
Test the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPODPNA2) structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPODPNA2 according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPODPNA2) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM)
3(DBFDPODPNA2) theoretical value: C is 75.94; H is 4.54; Eu is 7.69; N is 1.42; O is 7.28; And actual measured value: C is 76.12; H is 4.44; Eu is 7.54; N is 1.50; O is 7.42.
Use ultraviolet-visible pectrophotometer and FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph to testing the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPODPNA2) test, as shown in Figure 7, Fig. 7 is the synthetic Eu (DBM) of test 13
3(DBFDPODPNA2) Ultraluminescence spectrum; In Fig. 7-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 7, there is the characteristic emission peak of europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPODPNA2) measure, adopt KBr pressed disc method, test specification is 4000cm-
1～370cm-
1, as shown in figure 15, Figure 15 is the synthetic Eu (DBM) of test 13
3(DBFDPODPNA2) infrared spectrogram.As can be seen from Figure 15, at 3058cm
-1, 1632cm
-1and 1606cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1534cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in DBM, at 1519cm
-1, 1499cm
-1, 1477cm
-1and 1438cm
-1there is absorption peak at place, is the stretching vibration peak of C-P, at 1416cm
-1, 1351cm
-1, 1296cm
-1, 1222cm
-1, 1228cm
-1, 1198cm
-1, 1171cm
-1and 1124cm
-1there is absorption peak at place, is the stretching vibration peak of P=O.
Test 14: this test with test two differences is: the described luminescent layer of this test is the synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group of test 13
3(DBFDPODPNA2), the dopant material of PVK and PBD; In described luminescent layer, test the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPODPNA2) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 and Keithley2400 instrument to test the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group
3(DBFDPODPNA2) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 23, Figure 23 is the synthetic Eu (DBM) of test 14 use-testings 13
3(DBFDPODPNA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 23-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 23, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 31 is the synthetic Eu (DBM) of test 14 use-testings 13
3(DBFDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 31, the characteristic emission peak that 612nm place is Eu.
Test 15: this test with test one difference is: the beta-diketon described in step 1 is thienyl trifluoromethyl methyl ethyl diketone; The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPODPNA2; Described DBFDPODPNA2 structural formula is
other step and parameter are identical with test one.
Test the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that ten pentahaptos become
3(DBFDPODPNA2) structural formula is
the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 as DBFDPODPNA2 according to public announcement of a patent application number as: CN102898472A is prepared from;
The reaction formula of this test is as follows:
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that uses elemental analyser to become testing ten pentahaptos
3(DBFDPODPNA2) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA)
3(DBFDPODPNA2) theoretical value: C is 63.38; H is 3.48; Eu is 7.71; N is 1.42; O is 7.31; S is 4.88; And actual measured value: C is 63.51; H is 3.55; Eu is 7.68; N is 1.37; O is 7.46; S is 4.75.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that uses ultraviolet-visible pectrophotometer to become testing ten pentahaptos with FLSP920Combined Stead State Fluorescence and Phosphorescence Lifetime Spectrometer type spectrograph
3(DBFDPODPNA2) test, as shown in Figure 8, Fig. 8 is the Eu (TTA) that test ten pentahaptos become
3(DBFDPODPNA2) Ultraluminescence spectrum; In Fig. 8-and ■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.As can be seen from Figure 8, there is the characteristic emission peak of europium ion at 612nm place.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that uses Perkin-Elmer60000 infrared spectrometer to become testing ten pentahaptos
3(DBFDPODPNA2) measure, adopt KBr pressed disc method, test specification is 4000cm
-1～370cm
-1, as shown in figure 16, Figure 16 is the Eu (TTA) that test ten pentahaptos become
3(DBFDPODPNA2) infrared spectrogram.As can be seen from Figure 16, at 3057cm
-1and 1621cm
-1there is absorption peak at place, is the stretching vibration peak of C=O, at 1548cm
-1and 1531cm
-1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1484cm
-1and 1438cm
-1there is absorption peak at place, is the stretching vibration peak of C-P, at 1415cm
-1, 1322cm
-1, 1287cm
-1, 1176cm
-1, 1130cm
-1and 1072cm
-1there is absorption peak at place, is the stretching vibration peak of P=O.
Test 16: this test with test two differences is: the described luminescent layer of this test is the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that test ten pentahaptos become
3(DBFDPODPNA2), the dopant material of PVK and PBD; In described luminescent layer, test the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that ten pentahaptos become
3(DBFDPODPNA2) parts by weight are 5 parts, and the parts by weight of PVK are 65 parts, and the parts by weight of PBD are 30 parts.Other step and parameter are identical with test two.
Use PR650 and Keithley2400 instrument to the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) with the modification of triarylamine group becoming to test ten pentahaptos
3(DBFDPODPNA2) electroluminescent device of making as luminescent layer raw material is tested, and as shown in figure 24, Figure 24 is the Eu (TTA) that test 16 use-testing ten pentahaptos become
3(DBFDPODPNA2) as the electroluminescent device J-V-B curve of the luminescent layer material of electroluminescent device; In Figure 24-and-be current density voltage curve ,-■-be brightness-voltage curve, as shown in Figure 24, current density and brightness change with voltage change, can be applied in electroluminescent device.
Figure 32 is the Eu (TTA) that test 16 use-testing ten pentahaptos become
3(DBFDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.As can be seen from Figure 32, the characteristic emission peak that 612nm place is Eu.
Claims (10)
1. a dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group, it is characterized in that neutral ligand and beta-diketonate ligand complexing europium ion that a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is formed by the derivative of dibenzofuran group bidentate aromatic phosphines oxygen form, structure is:
wherein, described Ar
1during for H, Ar
2for
or with;
or Ar
1for
or
and Ar
1with Ar
2structural formula phase
Described R
1during for phenyl, R
2for phenyl;
Described R
1for CF
3time, R
2for α-thienyl.
2. preparation a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group as claimed in claim 1, is characterized in that a kind of synthetic method of the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is to carry out according to the following steps:
One, beta-diketon is dissolved in dehydrated alcohol, obtains beta-diketon/dehydrated alcohol mixing solutions;
The amount of substance of the beta-diketon described in step 1 and the volume ratio of dehydrated alcohol are (0.1mmol～0.2mmol): 1mL;
Two, six hydration europium chlorides are dissolved in distilled water, obtain the europium chloride aqueous solution;
Six amount of substances of hydration europium chloride described in step 2 and the volume ratio of distilled water are (0.5mmol～1.5mmol): 1mL;
Three, the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The amount of substance of dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 and the volume ratio of methylene dichloride are as 1mmol:(30mL～40mL);
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, under rate of titration is the condition of 5/min～10 droplet/min, the aqueous sodium hydroxide solution of 12mol/L～15mol/L is added drop-wise in container, be the 1h～3h that refluxes under the condition of 60 DEG C～70 DEG C in temperature, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min～10 droplet/min, be the 1h～3h that refluxes under the condition of 60 DEG C～70 DEG C in temperature, the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution that to modify with triarylamine group with the rate of titration of 5/min～10 droplet/min is again added drop-wise in container, be back flow reaction 12h～18h under the condition of 60 DEG C～70 DEG C in temperature, re-using Rotary Evaporators steams alcohol solvent, obtain powdery precipitate,
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and beta-diketon/dehydrated alcohol mixing solutions is (0.05～0.1): 1;
The volume ratio of the volume of the aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and the europium chloride aqueous solution is (1～1.5): 1;
In the amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with triarylamine group described in step 4 and beta-diketon/dehydrated alcohol mixing solutions, the amount of substance ratio of beta-diketon is as 1:3;
Five, powdery precipitate is used to distilled water filtering and washing 2 times～3 times, re-use dehydrated alcohol filtering and washing 2 times～3 times, be dry 6h～8h under the condition of 60 DEG C～70 DEG C in temperature again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group;
The dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 is as DBFDPOTPA, DBFDPODPNA, DBFDPOTPA2 or DBFDPODPNA2; Described DBFDPOTPA structural formula is
described DBFDPODPNA structural formula is
described DBFDPOTPA2 structural formula is
described DBFDPODPNA2 structural formula is
3. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that the beta-diketon described in step 1 is phenylbenzene methyl ethyl diketone or thienyl trifluoromethyl methyl ethyl diketone.
4. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that the amount of substance of the beta-diketon described in step 1 and the volume ratio of dehydrated alcohol are for (0.15mmol～0.2mmol): 1mL.
5. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that six amount of substances of hydration europium chloride described in step 2 and the volume ratio of distilled water are for (0.8mmol～1.5mmol): 1mL.
6. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that the volume of aqueous sodium hydroxide solution of the 12mol/L～15mol/L described in step 4 and the volume ratio of beta-diketon/dehydrated alcohol mixing solutions are (0.08～0.1): 1.
7. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that the volume of the aqueous sodium hydroxide solution described in step 4 and the volume ratio of the europium chloride aqueous solution are for (1.2～1.5): 1.
8. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that the amount of substance of dibenzofuran group bidentate aromatic phosphines oxygen part of modifying taking triarylamine group described in step 3 and the volume ratio of methylene dichloride are as 1mmol:(30mL～35mL).
9. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, it is characterized in that in step 5, powdery precipitate being used distilled water filtering and washing 2 times～3 times, re-use dehydrated alcohol filtering and washing 2 times～3 times, be dry 7h～8h under the condition of 65 DEG C～70 DEG C in temperature again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
10. the application of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group as claimed in claim 1, is characterized in that a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying using triarylamine group applies in electroluminescent device as luminescent layer material.
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| CN102898472A (en) * | 2012-11-02 | 2013-01-30 | 黑龙江大学 | Multifunctional modified dibenzofuran-based phosphineoxy compound and preparation method and application thereof |
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| CN102898472A (en) * | 2012-11-02 | 2013-01-30 | 黑龙江大学 | Multifunctional modified dibenzofuran-based phosphineoxy compound and preparation method and application thereof |
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