CN103980303A - Carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, synthesis method and applications thereof - Google Patents

Carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, synthesis method and applications thereof Download PDF

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CN103980303A
CN103980303A CN201410198216.3A CN201410198216A CN103980303A CN 103980303 A CN103980303 A CN 103980303A CN 201410198216 A CN201410198216 A CN 201410198216A CN 103980303 A CN103980303 A CN 103980303A
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bidentate aromatic
aromatic phosphines
phosphines oxygen
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modifying
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CN103980303B (en
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许辉
王鉴哲
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Heilongjiang University
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Heilongjiang University
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Abstract

The invention discloses a carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, a synthesis method and applications thereof, relates to a europium complex, a synthesis method and applications thereof, and aims to solve the problems that in the prior art the compatibility between a rare earth complex and a host material is bad; the complex and the host material are easy to break, and thus the device service life is affected; and the luminescent efficiency is low when the complex and the host material are applied to a luminescent device. The formula structure of the complex is shown in the description. A mixed solution of beta-diketone/absolute ethanol, a water solution of sodium hydroxide, a water solution of europium trichloride, and a mixed solution of carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide/dichloromethane are taken as the raw materials to prepare the carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, which can be used to prepare a luminescent layer in an electroluminescent device. The synthesis method provided by the invention can obtain a carbazolyl group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex.

Description

A kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex and synthetic method and application of modifying with carbazole group
Technical field
The present invention relates to a kind of europium complex and synthetic method thereof and application.
Background technology
People start from the sixties in 20th century to the research of electro optical phenomenon in organic materials field, P.Mkallmonn in 1963 adds more than 100 and lies prostrate after direct current on the monocrystalline of high fluorescence quantum efficiency organism anthracene, find that there is first organic electro luminescent phenomenon, and prepared simple electroluminescent device.But this progress of research is little for a long time, until just make a breakthrough for 1987.The C.W.Tang of Kodak has succeeded in developing with organic molecule 8-hydroxyquinoline aluminum (Alq 3) be the double-deck photodiode of luminescent layer, its driving voltage low (<10V), the large (1000cd/m of brightness 2), luminous efficiency high (1.51m/W).The people such as D.D.C.Bradley of univ cambridge uk be take conjugated polymers PPV and were made polymer LED as luminescent layer nineteen ninety.Compare with inorganic materials, luminous organic material device has advantages of that trigger voltage is low, luminous efficiency is high, low in energy consumption, flexible, response is fast, visual angle is wide, can large-area displays, color is complete, low cost of manufacture simultaneously, Commercial Prospect is very tempting, cause the great interest of people and extensive concern, and obtained significant progress.Up to the present, a large amount of rare earth compoundings are synthesized out, are broadly divided into two large classes: (1) rare earth organic molecule title complex; (2) rare earth high polymer title complex.Yet the problems such as rare earth organic molecule existence and stability is poor, these effects limit the application of rare earth luminescent material.
The luminescent layer of phosphorescent OLED normally adopts the material doped form of Subjective and Objective, wherein the transmission ofenergy between Subjective and Objective is the main path that phosphorescence twinkler is excited, and therefore selecting to absorb energy and the good material of main part of transferring energy is also an important channel of improving device performance.
It is poor that current existing rare earth compounding exists with material of main part consistency, is easily separated and affects device work-ing life, is applied to and in luminescent device, has the problem that luminous efficiency is low.
Summary of the invention
The object of the invention is to solve existing rare earth compounding and material of main part consistency is poor, easily be separated and affect device work-ing life, be applied to and in luminescent device, have 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 carbazole 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 carbazole 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 carbazole 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 carbazole group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group;
The take amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies and the volume ratio of methylene dichloride described in step 3 are 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, in temperature, be the 1h～3h that refluxes under the condition of 60 ℃～70 ℃, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min～10 droplet/min, in temperature, be the 1h～3h that refluxes under the condition of 60 ℃～70 ℃, rate of titration with 5/min～10 droplet/min is added drop-wise to dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group in container again, in temperature, be back flow reaction 12h～18h under the condition of 60 ℃～70 ℃, 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 that the carbazole group of take in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with carbazole group described in step 4 is modified 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, in temperature, be dry 6h～8h under the condition of 60 ℃～70 ℃ again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group;
The dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies of take described in step 3 is DBFDPOCz, DBFDPOPhCz, DBFDPOCz2 or DBFDPOPhCz2;
Described DBFDPOCz structural formula is described DBFDPOPhCz structural formula is described DBFDPOCz2 structural formula is described DBFDPOPhCz2 structural formula is
A kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of usining carbazole group modification is applied in electroluminescent device as luminescent layer material.
Advantage of the present invention: one, with the dibenzofuran group bidentate aromatic phosphines oxygen of modifying with carbazole group with subject characteristic as neutral ligand, the mode by coordination combines material of main part and guest materials, improves the transmission ofenergy between molecule;
Two, the present invention is when for electroluminescent device, and luminous efficiency is high, luminescent device purity of color is high, thereby has obtained the europium photoelectric functional material that a class has wide application prospect.
The present invention can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group.
Accompanying drawing explanation
Fig. 1 is the synthetic Eu (DBM) of test one 3(DBFDPOCz) 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(DBFDPOCz) 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(DBFDPOPhCz) 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(DBFDPOPhCz) 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(DBFDPOCz2) 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(DBFDPOCz2) 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(DBFDPOPhCz2) 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(DBFDPOPhCz2) 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(DBFDPOCz) infrared spectrogram;
Figure 10 is the synthetic Eu (TTA) of test three 3(DBFDPOCz) infrared spectrogram;
Figure 11 is the Eu (DBM) that test pentahapto becomes 3(DBFDPOPhCz) infrared spectrogram;
Figure 12 is the synthetic Eu (TTA) of test seven 3(DBFDPOPhCz) infrared spectrogram;
Figure 13 is the synthetic Eu (DBM) of test nine 3(DBFDPOCz2) infrared spectrogram;
Figure 14 is the synthetic Eu (TTA) of test 11 3(DBFDPOCz2) infrared spectrogram;
Figure 15 is the synthetic Eu (DBM) of test 13 3(DBFDPOPhCz2) infrared spectrogram;
Figure 16 is the synthetic Eu (TTA) of test ten the May 4ths 3(DBFDPOPhCz2) infrared spectrogram;
Figure 17 is the synthetic Eu (DBM) of test two use-testings one 3(DBFDPOCz) 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(DBFDPOCz) 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(DBFDPOPhCz) 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(DBFDPOPhCz) 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(DBFDPOCz2) 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(DBFDPOCz2) 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(DBFDPOPhCz2) 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(DBFDPOPhCz2) 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(DBFDPOCz) 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(DBFDPOCz) 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(DBFDPOPhCz) 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(DBFDPOPhCz) 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(DBFDPOCz2) 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(DBFDPOCz2) 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(DBFDPOPhCz2) 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(DBFDPOPhCz2) as the electroluminescent spectrogram of the electroluminescent device of the luminescent layer material of electroluminescent device.
Embodiment
Embodiment one: present embodiment neutral ligand and beta-diketonate ligand complexing europium ion that to be a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group 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.
The advantage of present embodiment: one, with the dibenzofuran group bidentate aromatic phosphines oxygen of modifying with carbazole group with subject characteristic as neutral ligand, the mode by coordination combines material of main part and guest materials, improves the transmission ofenergy between molecule;
Two, present embodiment is when for electroluminescent device, and luminous efficiency is high, luminescent device purity of color is high, thereby has obtained the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group.
Embodiment two: present embodiment is a kind of synthetic method of the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole 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 carbazole group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group;
The take amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies and the volume ratio of methylene dichloride described in step 3 are 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, in temperature, be the 1h～3h that refluxes under the condition of 60 ℃～70 ℃, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min～10 droplet/min, in temperature, be the 1h～3h that refluxes under the condition of 60 ℃～70 ℃, rate of titration with 5/min～10 droplet/min is added drop-wise to dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group in container again, in temperature, be back flow reaction 12h～18h under the condition of 60 ℃～70 ℃, 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 that the carbazole group of take in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with carbazole group described in step 4 is modified 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, in temperature, be dry 6h～8h under the condition of 60 ℃～70 ℃ again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group;
The take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modify of step described in three is DBFDPOCz, DBFDPOPhCz, DBFDPOCz2 or DBFDPOPhCz2;
Described DBFDPOCz structural formula is described DBFDPOPhCz structural formula is described DBFDPOCz2 structural formula is described DBFDPOPhCz2 structural formula is
The advantage of present embodiment: one, with the dibenzofuran group bidentate aromatic phosphines oxygen of modifying with carbazole group with subject characteristic as neutral ligand, the mode by coordination combines material of main part and guest materials, improves the transmission ofenergy between molecule;
Two, present embodiment is when for electroluminescent device, and luminous efficiency is high, luminescent device purity of color is high, thereby has obtained the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole 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: present embodiment and one of embodiment two or three difference are: 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 take amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies and the volume ratio of methylene dichloride described in step 3 are 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, in temperature, be dry 7h～8h under the condition of 65 ℃～70 ℃ again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group.Other steps are identical with embodiment two to eight.
Embodiment ten: present embodiment is to using the dibenzofuran group bidentate aromatic phosphines oxygen europium complex that carbazole group modifies to apply in electroluminescent device as luminescent layer material.
The advantage of present embodiment: one, with the dibenzofuran group bidentate aromatic phosphines oxygen of modifying with carbazole group with subject characteristic as neutral ligand, the mode by coordination combines material of main part and guest materials, improves the transmission ofenergy between molecule;
Two, present embodiment is when for electroluminescent device, and luminous efficiency is high, luminescent device purity of color is high, thereby has obtained the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: Eu (DBM) 3(DBFDPOCz) synthetic method of the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole 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 carbazole group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group;
The take amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies and the volume ratio of methylene dichloride described in step 3 are 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, in temperature, be the 1h that refluxes under the condition of 70 ℃, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min, in temperature, be the 1h that refluxes under the condition of 70 ℃, rate of titration with 5/min is added drop-wise to dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group in container again, in temperature, be back flow reaction 12h under the condition of 70 ℃, 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 that the carbazole group of take in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with carbazole group described in step 4 is modified 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-used dehydrated alcohol filtering and washing 3 times, then in temperature, be dry 8h under the condition of 70 ℃, obtain structural formula and be the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with carbazole group 3(DBFDPOCz).
Beta-diketon described in step 1 is phenylbenzene methyl ethyl diketone.
The dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies of take described in step 3 is DBFDPOCz, and described DBFDPOCz structural formula is described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOCz 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 carbazole group 3(DBFDPOCz) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBFDPOCz) theoretical value: C is 71.81; H is 4.28; Eu is 9.77; N is 0.90; O is 9.26; And actual observed value: C is 71.76; H is 4.15; Eu is 9.61; N is 0.93; O is 9.08.
Use ultraviolet-visible pectrophotometer and spectrograph to testing a synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with carbazole group 3(DBFDPOCz) test, as shown in Figure 1, Fig. 1 is the synthetic Eu (DBM) of test one 3(DBFDPOCz) 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, the characteristic emission peak that has 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 carbazole group 3(DBFDPOCz) 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(DBFDPOCz) infrared spectrogram.As can be seen from Figure 9, at 3053cm -1, 1964cm -1and 1596cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1551cm -1there is absorption peak at place, is the stretching vibration peak of C=C in DBM, at 1518cm -1, 1465cm -1and 1438cm -1having absorption peak, is the stretching vibration peak of C-P, at 1421cm -1, 1308cm -1, 1265cm -1, 1237cm -1, 1217cm -1, 1202cm -1and 1179cm -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 to film, and hole transmission layer and luminescent layer adopt spin coating technique to 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 carbazole 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 carbazole group of test one 3(DBFDPOCz), 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 carbazole group 3(DBFDPOCz) 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 to film, and hole transmission layer and luminescent layer adopt spin coating technique to 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 carbazole group 3(DBFDPOCz) 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(DBFDPOCz) 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(DBFDPOCz) 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 carbazole group that test three obtains 3(DBFDPOCz) structural formula is
The reaction formula of test three is as follows:
Use elemental analyser to testing the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with carbazole group 3(DBFDPOCz) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3(DBFDPOCz) theoretical value: C is 55.82; H is 2.93; Eu is 9.81; N is 0.90; O is 9.29; S is 6.21; And actual measured value: C is 55.93; H is 2.74; Eu is 9.72; N is 0.84; O is 9.39; S is 6.36.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with carbazole group 3(DBFDPOCz) test, as shown in Figure 2, Fig. 2 is the synthetic Eu (TTA) of test three 3(DBFDPOCz) Ultraluminescence spectrum, in Fig. 2-■-be ultra-violet absorption spectrum curve ,--be the fluorescence radiation curve of spectrum.At 612nm place, there is as can be seen from Figure 2 the characteristic emission peak of europium ion.
Use Perkin-Elmer60000 infrared spectrometer to testing the three synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with carbazole group 3(DBFDPOCz) 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(DBFDPOCz) infrared spectrogram.As can be seen from Figure 10, at 3057cm -1, 1970cm -1and 1568cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1520cm -1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1501cm -1, 1467cm -1and 1438cm -1having absorption peak, is the stretching vibration peak of C-P, at 1414cm -1, 1353cm -1, 1302cm -1, 1245cm -1, 1230cm -1, 1170cm -1and 1134cm -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 carbazole group of test three 3(DBFDPOCz), 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 carbazole group 3(DBFDPOCz) 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 carbazole group 3(DBFDPOCz) 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(DBFDPOCz) 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(DBFDPOCz) 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 carbazole group modification of take described in step 3 is DBFDPOPhCz; The structural formula of described DBFDPOPhCz is other step and parameter are identical with test one.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with carbazole group that test pentahapto becomes 3(DBFDPOPhCz) structural formula is
Described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOPhCz 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 carbazole group that uses elemental analyser to become test pentahapto 3(DBFDPOPhCz) carry out ultimate analysis test, obtain data as follows:
Eu (DBM) 3(DBFDPOPhCz) theoretical value: C is 72.88; H is 4.32; Eu is 9.31; N is 0.86; O is 8.83; And actual measured value: C is 72.69; H is 4.54; Eu is 9.13; N is 0.88; O is 8.67.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with carbazole group that uses ultraviolet-visible pectrophotometer with spectrograph, test pentahapto to be become 3(DBFDPOPhCz) test, as shown in Figure 3, Fig. 3 is that test pentahapto becomes Eu (DBM) 3(DBFDPOPhCz) 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, the characteristic emission peak that has europium ion at 612nm place.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with carbazole group that uses Perkin-Elmer60000 infrared spectrometer to become test pentahapto 3(DBFDPOPhCz) 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(DBFDPOPhCz) infrared spectrogram.As can be seen from Figure 11, at 3054cm -1, 2950cm -1, 1955cm -1and 1602cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1561cm -1there is absorption peak at place, is the stretching vibration peak of C=C in DBM, at 1514cm -1and 1465cm -1having absorption peak, is the stretching vibration peak of C-P, at 1424cm -1, 1399cm -1, 1309cm -1, 1277cm -1, 1220cm -1and 1194cm -1having absorption peak, is the stretching vibration peak of P=O.
Test six: this test with test two differences is: the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with carbazole group that the described luminescent layer of this test becomes for test pentahapto 3(DBFDPOPhCz), 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 carbazole group that pentahapto becomes 3(DBFDPOPhCz) 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 with Keithley2400 instrument to the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) with carbazole group modification becoming with test pentahapto 3(DBFDPOPhCz) 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(DBFDPOPhCz) 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(DBFDPOPhCz) 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 that carbazole group modifies of take described in step 3 is DBFDPOPhCz; Described DBFDPOPhCz 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 carbazole group that test seven is synthetic 3(DBFDPOPhCz) structural formula is described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOPhCz 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 carbazole group 3(DBFDPOPhCz) carry out ultimate analysis test, obtain data as follows:
Eu (TTA) 3(DBFDPOPhCz) theoretical value: C is 57.64; H is 3.04; Eu is 9.35; N is 0.86; O is 8.86; S is 5.92; And actual measured value: C is 57.71; H is 2.89; Eu is 9.14; N is 0.95; O is 8.62; S is 5.70.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with carbazole group 3(DBFDPOPhCz) test, as shown in Figure 4, Fig. 4 is the synthetic Eu (TTA) of test seven 3(DBFDPOPhCz) 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, the characteristic emission peak that has 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 carbazole group 3(DBFDPOPhCz) 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(DBFDPOPhCz) infrared spectrogram.As can be seen from Figure 12, at 3055cm -1and 1595cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1545cm -1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1517cm -1, 1478cm -1and 1454cm -1having absorption peak, is the stretching vibration peak of C-P, at 1399cm -1, 1306cm -1, 1219cm -1and 1163cm -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 test seven synthetic the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) 3 (DBFDPOPhCz), the PVK that modify with carbazole group and the dopant material of PBD; In described luminescent layer, test the seven synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with carbazole group 3(DBFDPOPhCz) 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 carbazole group 3(DBFDPOPhCz) 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(DBFDPOPhCz) 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(DBFDPOPhCz) 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 carbazole group modification of take described in step 3 is DBFDPOCz2; Described DBFDPOCz2 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 carbazole group that test nine is synthetic 3(DBFDPOCz2) structural formula is described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOCz2 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 carbazole group 3(DBFDPOCz2) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBFDPOCz2) theoretical value: C is 73.29; H is 4.38; Eu is 8.83; N is 1.63; O is 8.37; And actual measured value: C is 73.03; H is 4.56; Eu is 8.68; N is 1.71; O is 8.21.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with carbazole group 3(DBFDPOCz2) test, as shown in Figure 5, Fig. 5 is the synthetic Eu (DBM) of test nine 3(DBFDPOCz2) 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, the characteristic emission peak that 612nm place is Eu.
Use Perkin-Elmer60000 infrared spectrometer to testing the nine synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with carbazole group 3(DBFDPOCz2) 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(DBFDPOCz2) infrared spectrogram.As can be seen from Figure 13, at 3058cm -1and 1624cm -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 1464cm -1, 1498cm -1, 1468cm -1and 1453cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm -1, 1291cm -1, 1183cm -1and 1134cm -1having absorption peak, 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 carbazole group of test nine 3(DBFDPOCz2), 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 carbazole group 3(DBFDPOCz2) 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 carbazole group 3(DBFDPOCz2) 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(DBFDPOCz2) 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 that test ten use-testings are tested nine synthetic Eu (DBM) 3(DBFDPOCz2) 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 that carbazole group modifies of take described in step 3 is DBFDPOCz2; Described DBFDPOCz2 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 carbazole group 3(DBFDPOCz2) structural formula is described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOCz2 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 carbazole group 3(DBFDPOCz2) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3(DBFDPOCz2) theoretical value: C is 58.85; H is 3.06; Eu is 8.86; N is 1.63; O is 8.40; S is 5.61; And actual observed value: C is 58.77; H is 3.12; Eu is 8.65; N is 1.71; O is 8.22; S is 5.53.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the 11 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with carbazole group 3(DBFDPOCz2) test, as shown in Figure 6, Fig. 6 is the synthetic Eu (TTA) of test 11 3(DBFDPOCz2) 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, the characteristic emission peak that has 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 carbazole group 3(DBFDPOCz2) 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(DBFDPOCz2) infrared spectrogram.As can be seen from Figure 14, at 3058cm -1and 1624cm -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 1522cm -1, 1492cm -1, 1464cm -1and 1453cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm -1, 1357cm -1, 1292cm -1, 1184cm -1and 1134cm -1having absorption peak, 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 carbazole group of test 11 3(DBFDPOCz2), 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 carbazole group 3(DBFDPOCz2) 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 carbazole group 3(DBFDPOCz2) 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(DBFDPOCz2) 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-testing test 11 3(DBFDPOCz2) 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 that carbazole group modifies of take described in step 3 is DBFDPOPhCz2; Described DBFDPOPhCz2 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 carbazole group 3(DBFDPOPhCz2) structural formula is described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOPhCz2 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 carbazole group 3(DBFDPOPhCz2) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBFDPOPhCz2) theoretical value: C is 5.03; H is 4.36; Eu is 8.11; N is 1.50; O is 7.69; And actual measured value: C is 75.25; H is 4.22; Eu is 8.23; N is 1.54; O is 7.61.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the 13 synthetic dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with carbazole group 3(DBFDPOPhCz2) test, as shown in Figure 7, Fig. 7 is the synthetic Eu (DBM) of test 13 3(DBFDPOPhCz2) 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, the characteristic emission peak that has 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 carbazole group 3(DBFDPOPhCz2) 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(DBFDPOPhCz2) infrared spectrogram.As can be seen from Figure 15, at 3056cm -1and 1595cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1548cm -1there is absorption peak at place, is the stretching vibration peak of C=C in DBM, at 1518cm -1, 1478cm -1, 1455cm -1and 1437cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1402cm -1, 1308cm -1, 1219cm -1, 1143cm -1and 1102cm -1having absorption peak, 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 carbazole group of test 13 3(DBFDPOPhCz2), 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 carbazole group 3(DBFDPOPhCz2) 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 carbazole group 3(DBFDPOPhCz2) 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(DBFDPOPhCz2) 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(DBFDPOPhCz2) 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 that carbazole group modifies of take described in step 3 is DBFDPOPhCz2; Described DBFDPOPhCz2 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 carbazole group that ten pentahaptos become 3(DBFDPOPhCz2) structural formula is described in step 3 take dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies as DBFDPOPhCz2 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 carbazole group that uses elemental analyser to become testing ten pentahaptos 3(DBFDPOPhCz2) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3(DBFDPOPhCz2) observed value: C is 61.77; H is 3.24; Eu is 8.14; N is 1.50; O is 7.71; S is 5.15; And theoretical value: C is 61.76; H is 3.17; Eu is 8.01; N is 1.62; O is 7.65; S is 5.02.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with carbazole group that uses ultraviolet-visible pectrophotometer to become testing ten pentahaptos with spectrograph 3(DBFDPOPhCz2) test, as shown in Figure 8, Fig. 8 is the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with carbazole group that test ten pentahaptos become 3(DBFDPOPhCz2) 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, the characteristic emission peak that has europium ion at 612nm place.
The dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with carbazole group that uses Perkin-Elmer60000 infrared spectrometer to become testing ten pentahaptos 3(DBFDPOPhCz2) 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(DBFDPOPhCz2) infrared spectrogram.As can be seen from Figure 16, at 3059cm -1, 1625cm -1and 1589cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1549cm -1and 1533cm -1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1437cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1405cm -1, 1324cm -1, 1292cm -1, 1220cm -1, 1184cm -1and 1133cm -1having absorption peak, is the stretching vibration peak of P=O.
Test 16: this test with test two differences is: the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with carbazole group that the described luminescent layer of this test becomes for test ten pentahaptos 3(DBFDPOPhCz2), 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 carbazole group that ten pentahaptos become 3(DBFDPOPhCz2) 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 with Keithley2400 instrument to the dibenzofuran group bidentate aromatic phosphines oxygen europium complex Eu (TTA) with carbazole group modification becoming to test ten pentahaptos 3(DBFDPOPhCz2) 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(DBFDPOPhCz2) 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(DBFDPOPhCz2) 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 carbazole 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 carbazole 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 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.
2. prepare a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group as claimed in claim 1, it is characterized in that a kind of synthetic method of the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole 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 carbazole group is dissolved in methylene dichloride, obtains dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group;
The take amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies and the volume ratio of methylene dichloride described in step 3 are 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, in temperature, be the 1h～3h that refluxes under the condition of 60 ℃～70 ℃, then the europium chloride aqueous solution is added drop-wise in container under the rate of titration with 5/min～10 droplet/min, in temperature, be the 1h～3h that refluxes under the condition of 60 ℃～70 ℃, rate of titration with 5/min～10 droplet/min is added drop-wise to dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with carbazole group in container again, in temperature, be back flow reaction 12h～18h under the condition of 60 ℃～70 ℃, 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 that the carbazole group of take in the dibenzofuran group bidentate aromatic phosphines oxygen part/dichloromethane solution modified with carbazole group described in step 4 is modified 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, in temperature, be dry 6h～8h under the condition of 60 ℃～70 ℃ again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group;
The dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies of take described in step 3 is DBFDPOCz, DBFDPOPhCz, DBFDPOCz2 or DBFDPOPhCz2;
Described DBFDPOCz structural formula is described DBFDPOPhCz structural formula is described DBFDPOCz2 structural formula is described DBFDPOPhCz2 structural formula is
3. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole 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 carbazole 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 carbazole 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 carbazole 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 carbazole 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 carbazole group according to claim 2, is characterized in that the take amount of substance of the dibenzofuran group bidentate aromatic phosphines oxygen part that carbazole group modifies and the volume ratio of methylene dichloride described in step 3 is 1mmol:(30mL～35mL).
9. the synthetic method of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group according to claim 2, it is characterized in that powdery precipitate being used to distilled water filtering and washing 2 times～3 times in step 5, re-use dehydrated alcohol filtering and washing 2 times～3 times, in temperature, be dry 7h～8h under the condition of 65 ℃～70 ℃ again, obtain the dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group.
10. the application of a kind of dibenzofuran group bidentate aromatic phosphines oxygen europium complex of modifying with carbazole group as claimed in claim 1, is characterized in that a kind ofly usining the dibenzofuran group bidentate aromatic phosphines oxygen europium complex that carbazole group modifies and applying in electroluminescent device as luminescent layer material.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687080A (en) * 2005-04-14 2005-10-26 复旦大学 Rare earth complexes chelated by aromatic base substituted diphosphine dioxide and its synthesizing process
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687080A (en) * 2005-04-14 2005-10-26 复旦大学 Rare earth complexes chelated by aromatic base substituted diphosphine dioxide and its synthesizing process
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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