CN103980302A - Triarylamino group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, synthesis method and applications thereof - Google Patents

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

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CN103980302A
CN103980302A CN201410198143.8A CN201410198143A CN103980302A CN 103980302 A CN103980302 A CN 103980302A CN 201410198143 A CN201410198143 A CN 201410198143A CN 103980302 A CN103980302 A CN 103980302A
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bidentate aromatic
aromatic phosphines
dibenzothiophene base
phosphines oxygen
test
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CN103980302B (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 triarylamino 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 (1) the chemical stability and cavity transporting ability of a rare earth complex are bad; (2) when a rare earth material is applied to an electroluminescent device, the rare earth material and the host material are easy to separate, and thus the luminescent efficiency of the electroluminescent device is low. The structural formula of the complex is represented in the description. A mixed solution of beta-diketone/absolute ethanol, a water solution of europium trichloride, and a mixed solution of triarylamino group modified dibenzofuryl bidentate aromatic phosphine oxide complex/dichloromethane are taken as the raw materials to prepare the triarylamino group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex, which is used to prepare a luminescent layer in an electroluminescent device. The synthesis method provided by the invention can produce a triarylamino group modified dibenzofuryl bidentate aromatic phosphine oxide europium complex.

Description

A kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex and synthetic method and application of modifying with triarylamine group
Technical field
The present invention relates to a kind of europium complex and synthetic method thereof and application.
Background technology
Rare earth compounding emission band is narrow, and emmission spectrum has class atomic spectrum character, and purity of color high (half broad peak <10nm) is very suitable for full color and shows.In addition, rare earth compounding luminous efficiency is high, and internal quantum efficiency can reach 100% in theory.Therefore, rare earth compounding is one of luminescent material desirable in panchromatic flat-panel display device, and research rare earth compounding Electroluminescence Properties has important practical significance and theory significance.
In recent years, rare earth organic complex is owing to having advantages of good monochromaticity, be widely used in preparing electroluminescent device, but up to the present, it as electroluminescent rare earth organic complex, is mainly the organic coordination compound of europium, terbium, and rare-earth organic electroluminescence device in performance far from and other using small molecule material and polymer materials as the El element of luminescent layer, this be because: chemical stability and the fluorescent stability of rare earth compounding are poor, can not make high-quality film; Device luminous efficiency is low, and most of electric energy conversion is heat energy etc.; The normal sharp compound transmitting of base, the severe jamming Line Emission of occurring of rare earth electroluminescent device; Device lifetime is short.
Therefore, existing rare earth compounding exist chemical stability and cavity transmission ability poor, rare earth compounding is applied in electroluminescent device and exists easily and material of main part is separated, the problem that luminous efficiency is low.
Summary of the invention
The object of the invention is to solve existing rare earth compounding exist chemical stability and cavity transmission ability poor, rare earth compounding is applied in electroluminescent device and exists easily and material of main part is separated, the problem that luminous efficiency is low, and a kind of dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is formed by the derivative of dibenzothiophene base bidentate aromatic phosphines oxygen form, and structure is:
wherein, described Ar 1during for H, for 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 kind of synthetic method of the dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The take amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group described in step 4, take the amount of substance ratio of beta-diketon in amount of substance and beta-diketon/dehydrated alcohol mixing solutions of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group;
The dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPOTPA, DBTDPODPNA, DBTDPOTPA2 or DBTDPODPNA2; Described DBTDPOTPA structural formula is described DBTDPODPNA structural formula is described DBTDPOTPA2 structural formula is described DBTDPODPNA2 structural formula is
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex that the triarylamine of usining group modifies is applied in electroluminescent device as luminescent layer material.
Advantage of the present invention: one, material of main part and guest materials are combined, improve the energy transfer efficiency between molecule, conjugated system has increased steric effect more greatly simultaneously, reduces the self quenching of triplet excitons;
Two, the present invention is when the electroluminescent device, the transmission that the introducing of cavity transmission group can equilbrium carrier, improves luminous efficiency, thereby obtained the europium photoelectric functional material that a class has wide application prospect.
The present invention can obtain a kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
Accompanying drawing explanation
Fig. 1 is the synthetic Eu (DBM) of test one 3(DBTDPOTPA) 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(DBTDPOTPA) 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(DBTDPODPNA) 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(DBTDPODPNA) 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(DBTDPOTPA2) 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(DBTDPOTPA2) 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(DBTDPODPNA2) 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(DBTDPODPNA2) 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(DBTDPOTPA) infrared spectrogram;
Figure 10 is the synthetic Eu (TTA) of test three 3(DBTDPOTPA) infrared spectrogram;
Figure 11 is the Eu (DBM) that test pentahapto becomes 3(DBTDPODPNA) infrared spectrogram;
Figure 12 is the synthetic Eu (TTA) of test seven 3(DBTDPODPNA) infrared spectrogram;
Figure 13 is the synthetic Eu (DBM) of test nine 3(DBTDPOTPA2) infrared spectrogram;
Figure 14 is the synthetic Eu (TTA) of test 11 3(DBTDPOTPA2) infrared spectrogram;
Figure 15 is the synthetic Eu (DBM) of test 13 3(DBTDPODPNA2) infrared spectrogram;
Figure 16 is the Eu (TTA) that test ten pentahaptos become 3(DBTDPODPNA2) infrared spectrogram;
Figure 17 is the synthetic Eu (DBM) of test two use-testings one 3(DBTDPOTPA) 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(DBTDPOTPA) 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(DBTDPODPNA) 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(DBTDPODPNA) 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(DBTDPOTPA2) 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(DBTDPOTPA2) 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(DBTDPODPNA2) 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(DBTDPODPNA2) 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(DBTDPOTPA) 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(DBTDPOTPA) 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(DBTDPODPNA) 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(DBTDPODPNA) 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(DBTDPOTPA2) 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(DBTDPOTPA2) 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(DBTDPODPNA2) 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(DBTDPODPNA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group formed by the derivative of dibenzothiophene base bidentate aromatic phosphines oxygen form, and structure is:
wherein, described Ar 1during for H, for 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, material of main part and guest materials are combined, improve the energy transfer efficiency between molecule, conjugated system has increased steric effect more greatly simultaneously, reduces the self quenching of triplet excitons;
Two, present embodiment is when the electroluminescent device, the transmission that the introducing of cavity transmission group can equilbrium carrier, improves luminous efficiency, thereby obtained the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
Embodiment two: present embodiment is that a kind of synthetic method of the dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The take amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group described in step 4, take the amount of substance ratio of beta-diketon in amount of substance and beta-diketon/dehydrated alcohol mixing solutions of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group;
The dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPOTPA, DBTDPODPNA, DBTDPOTPA2 or DBTDPODPNA2; Described DBTDPOTPA structural formula is described DBTDPODPNA structural formula is described DBTDPOTPA2 structural formula is described DBTDPODPNA2 structural formula is
The advantage of present embodiment: one, material of main part and guest materials are combined, improve the energy transfer efficiency between molecule, conjugated system has increased steric effect more greatly simultaneously, reduces the self quenching of triplet excitons;
Two, present embodiment is when the electroluminescent device, the transmission that the introducing of cavity transmission group can equilbrium carrier, improves luminous efficiency, thereby obtained the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of dibenzothiophene base 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: 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 dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine 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 dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of usining the modification of 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(DBTDPOTPA) synthetic method of the dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The take amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group described in step 4, take the amount of substance ratio of beta-diketon in amount of substance and beta-diketon/dehydrated alcohol mixing solutions of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group 3(DBTDPOTPA).
Beta-diketon described in step 1 is phenylbenzene methyl ethyl diketone;
The dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPOTPA, and described DBTDPOTPA structural formula is described in step 4 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPOTPA according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of test one is as follows:
Use elemental analyser to testing a synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group 3(DBTDPOTPA) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBTDPOTPA) theoretical value: C is 72.08; H is 4.40; Eu is 9.21; N is 0.85; O is 7.76; S is 1.94; And actual measured value: C is 71.86; H is 4.34; Eu is 9.29; N is 0.77; O is 7.73; S is 2.06.
Use ultraviolet-visible pectrophotometer and spectrograph to testing a synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group 3(DBTDPOTPA) test, as shown in Figure 1, Fig. 1 is the synthetic Eu (DBM) of test one 3(DBTDPOTPA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group 3(DBTDPOTPA) 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(DBTDPOTPA) infrared spectrogram.As can be seen from Figure 9, at 3056cm -1and 1594cm -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 DBM, at 1517cm -1, 1478cm -1and 1456cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1406cm -1, 1308cm -1, 1220cm -1, 1166cm -1, 1120cm -1and 1099cm -1there is absorption peak at place, 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 dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group of test one 3(DBTDPOTPA), the dopant material of PVK and PBD; In luminescent layer described in test two, test a synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group 3(DBTDPOTPA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) who modifies with triarylamine group 3(DBTDPOTPA) 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(DBTDPOTPA) 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(DBTDPOTPA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that test three is synthetic 3(DBTDPOTPA) structural formula is
The reaction formula of this test is as follows:
Use elemental analyser to testing the three synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3(DBTDPOTPA) theoretical value: C is 57.01; H is 3.13; Eu is 9.25; N is 0.85; O is 7.79; S is 7.80; And actual observed value: C is 57.16; H is 3.29; Eu is 9.14; N is 0.92; O is 7.85; S is 7.71.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the three synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA) test, as shown in Figure 2, Fig. 2 is the synthetic Eu (TTA) of test three 3(DBTDPOTPA) 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, the characteristic emission peak that has europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the three synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA) 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(DBTDPOTPA) infrared spectrogram.As can be seen from Figure 10, at 3060cm -1, 1616cm -1and 1573cm -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 1515cm -1, 1498cm -1, 1480cm -1and 1437cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm -1, 1358cm -1, 1302cm -1, 1240cm -1, 1228cm -1, 1179cm -1, 1164cm -1, 1139cm -1and 1102cm -1there is absorption peak at place, 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group of test three 3(DBTDPOTPA), the dopant material of PVK and PBD; In described luminescent layer, test the three synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA) 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(DBTDPOTPA) 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(DBTDPOTPA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen part of triarylamine group modification of take described in step 3 is DBTDPODPNA; Described DBTDPODPNA structural formula is other step and parameter are identical with test one.
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that test pentahapto becomes 3(DBTDPODPNA) structural formula is described in step 3 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPODPNA according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of this test is as follows:
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that uses elemental analyser to become test pentahapto 3(DBTDPODPNA) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBTDPODPNA) theoretical value: C is 72.78; H is 4.39; Eu is 8.94; N is 0.82; O is 7.53; S is 1.89; And actual observed value: C is 72.89; H is 4.34; Eu is 9.12; N is 0.97; O is 7.57; S is 1.74.
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that uses ultraviolet-visible pectrophotometer with spectrograph, test pentahapto to be become 3(DBTDPODPNA) test, as shown in Figure 3, Fig. 3 is the Eu (DBM) that test pentahapto becomes 3(DBTDPODPNA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that uses Perkin-Elmer60000 infrared spectrometer to become test pentahapto 3(DBTDPODPNA) 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(DBTDPODPNA) infrared spectrogram.As can be seen from Figure 11, at 3057cm -1and 1620cm -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 1496cm -1, 1461cm -1and 1437cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1402cm -1, 1360cm -1, 1323cm -1, 1287cm -1, 1219cm -1, 1169cm -1, and 1131cm -1there is absorption peak at place, is the stretching vibration peak of P=O.
Test six: this test with test two differences is: the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that the described luminescent layer of this test becomes for test pentahapto 3(DBTDPODPNA), the dopant material of PVK and PBD; In described luminescent layer, test the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that pentahapto becomes 3(DBTDPODPNA) 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 what become with test pentahapto, with triarylamine, to roll into a ball the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with Keithley2400 instrument 3(DBTDPODPNA) 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(DBTDPODPNA) 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(DBTDPODPNA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPODPNA; Described DBTDPODPNA structural formula is other step and parameter are identical with test one.
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that test seven is synthetic 3(DBTDPODPNA) structural formula is described in step 3 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPODPNA according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the seven synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPODPNA) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3(DBTDPODPNA) theoretical value: C is 58.16; H is 3.15; Eu is 8.97; N is 0.83; O is 7.56; S is 7.57; And actual observed value: C is 58.20; H is 3.03; Eu is 9.08; N is 0.78; O is 7.39; S is 7.64.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the seven synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPODPNA) test, as shown in Figure 4, Fig. 4 is the synthetic Eu (TTA) of test seven 3(DBTDPODPNA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPODPNA) 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(DBTDPODPNA) infrared spectrogram.As can be seen from Figure 12, at 3053cm -1and 1595cm -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 TTA, at 1517cm -1, 1477cm -1and 1437cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1419cm -1, 1307cm -1, 1265cm -1, 1236cm -1, 1217cm -1, 1193cm -1, 1178cm -1and 1120cm -1there is absorption peak at place, 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group of test seven 3(DBTDPODPNA), the dopant material of PVK and PBD; In described luminescent layer, test the seven synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPODPNA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPODPNA) 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(DBTDPODPNA) 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(DBTDPODPNA) 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 dibenzothiophene base bidentate aromatic phosphines oxygen part of triarylamine group modification of take described in step 3 is DBTDPOTPA2; Described DBTDPOTPA2 structural formula is other step and parameter are identical with test one.
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group that test nine is synthetic 3(DBTDPOTPA2) structural formula is described in step 3 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPOTPA2 according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the nine synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPOTPA2) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBTDPOTPA2) theoretical value: C is 74.24; H is 4.53; Eu is 8.03; N is 1.48; O is 6.76; S is 1.69; And actual observed value: C is 74.48; H is 4.36; Eu is 8.24; N is 1.55; O is 6.67; S is 1.62.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the nine synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPOTPA2) test, as shown in Figure 5, Fig. 5 is the synthetic Eu (DBM) of test nine 3(DBTDPOTPA2) 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 has europium ion at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to testing the nine synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPOTPA2) 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(DBTDPOTPA2) infrared spectrogram.As can be seen from Figure 13, at 3062cm -1and 1612cm -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 DBM, at 1513cm -1, 1488cm -1and 1458cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm -1, 1359cm -1, 1309cm -1, 1230cm -1, 1228cm -1and 1181cm -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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group of test nine 3(DBTDPOTPA2), the dopant material of PVK and PBD; In described luminescent layer, test the nine synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPOTPA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPOTPA2) 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(DBTDPOTPA2) 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(DBTDPOTPA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPOTPA2; Described DBTDPOTPA2 structural formula is other step and parameter are identical with test one.
Test the 11 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA2) structural formula is described in step 3 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPOTPA2 according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the 11 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA2) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3(DBTDPOTPA2) theoretical value: C is 61.11; H is 3.42; Eu is 8.05; N is 1.48; O is 6.78; S is 6.80; And actual observed value: C is 60.95; H is 3.51; Eu is 8.08; N is 1.54; O is 6.64; S is 6.75.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the 11 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA2) test, as shown in Figure 6, Fig. 6 is the synthetic Eu (TTA) of test 11 3(DBTDPOTPA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA2) 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(DBTDPOTPA2) infrared spectrogram.As can be seen from Figure 14, at 3058cm -1and 1620cm -1there is absorption peak at place, is the stretching vibration peak of C=O, at 1533cm -1there is absorption peak at place, is the stretching vibration peak of C=C in TTA, at 1509cm -1, 1483cm -1and 1463cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm -1, 1357cm -1, 1301cm -1, 1288cm -1and 1136cm -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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group of test 11 3(DBTDPOTPA2), the dopant material of PVK and PBD; In described luminescent layer, test the 11 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) that modify with triarylamine group 3(DBTDPOTPA2) 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(DBTDPOTPA2) 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(DBTDPOTPA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPODPNA2; Described DBTDPODPNA2 structural formula is other step and parameter are identical with test one.
Test the 13 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPODPNA2) structural formula is described in step 3 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPODPNA2 according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to testing the 13 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPODPNA2) carry out ultimate analysis test, obtain data as follows:
For Eu (DBM) 3(DBTDPODPNA2) theoretical value: C is 5.33; H is 4.50; Eu is 7.62; N is 1.41; O is 6.42; S is 1.61; And actual observed value: C is 75.58; H is 4.48; Eu is 7.69; N is 1.24; O is 6.61; S is 1.69.
Use ultraviolet-visible pectrophotometer and spectrograph to testing the 13 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPODPNA2) test, as shown in Figure 7, Fig. 7 is the synthetic Eu (DBM) of test 13 3(DBTDPODPNA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPODPNA2) 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(DBTDPODPNA2) infrared spectrogram.As can be seen from Figure 15, at 3055cm -1and 1594cm -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 1515cm -1, 1477cm -1and 1455cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1404cm -1, 1306cm -1, 1218cm -1, 1172cm -1and 1118cm -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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) modifying with triarylamine group of test 13 3(DBTDPODPNA2), the dopant material of PVK and PBD; In described luminescent layer, test the 13 synthetic dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPODPNA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) that modify with triarylamine group 3(DBTDPODPNA2) 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(DBTDPODPNA2) 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(DBTDPODPNA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPODPNA2; Described DBTDPODPNA2 structural formula is other step and parameter are identical with test one.
Test the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that ten pentahaptos become 3(DBTDPODPNA2) structural formula is described in step 3 take dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies as DBTDPODPNA2 according to public announcement of a patent application number as: CN102898473A is prepared from;
The reaction formula of this test is as follows:
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that uses elemental analyser to become testing ten pentahaptos 3(DBTDPODPNA2) carry out ultimate analysis test, obtain data as follows:
For Eu (TTA) 3dBTDPODPNA2) theoretical value: C is 62.87; H is 3.45; Eu is 7.65; N is 1.41; O is 6.44; S is 6.46; And actual observed value: C is 62.78; H is 3.45; Eu is 7.44; N is 1.56; O is 6.38; S is 6.34.
The dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that uses ultraviolet-visible pectrophotometer to become testing ten pentahaptos with spectrograph 3(DBTDPODPNA2) test, as shown in Figure 8, Fig. 8 is the Eu (TTA) that test ten pentahaptos become 3(DBTDPODPNA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that uses Perkin-Elmer60000 infrared spectrometer to become testing ten pentahaptos 3(DBTDPODPNA2) 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(DBTDPODPNA2) infrared spectrogram.As can be seen from Figure 16, at 3057cm -1, 1608cm -1and 1568cm -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 TTA, at 1501cm -1, 1467cm -1and 1438cm -1there is absorption peak at place, is the stretching vibration peak of C-P, at 1414cm -1, 1353cm -1, 1302cm -1, 1245cm -1, 1230cm -1, 1170cm -1and 1134cm -1there is absorption peak at place, is the stretching vibration peak of P=O.
Test 16: this test with test two differences is: the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that the described luminescent layer of this test becomes for test ten pentahaptos 3(DBTDPODPNA2), the dopant material of PVK and PBD; In described luminescent layer, test the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) modifying with triarylamine group that ten pentahaptos become 3(DBTDPODPNA2) 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) with the modification of triarylamine group becoming to test ten pentahaptos 3(DBTDPODPNA2) 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(DBTDPODPNA2) 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(DBTDPODPNA2) 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. with triarylamine, roll into a ball the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying for one kind, it is characterized in that neutral ligand and beta-diketonate ligand complexing europium ion that a kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group is formed by the derivative of dibenzothiophene base bidentate aromatic phosphines oxygen form, structure is:
wherein, described Ar 1during for H, for 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group as claimed in claim 1, it is characterized in that a kind of synthetic method of the dibenzothiophene base 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 dibenzothiophene base bidentate aromatic phosphines oxygen part of modifying with triarylamine group is dissolved in methylene dichloride, obtains dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group;
The take amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of modifying with triarylamine group described in step 4, take the amount of substance ratio of beta-diketon in amount of substance and beta-diketon/dehydrated alcohol mixing solutions of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group;
The dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine group modifies of take described in step 3 is DBTDPOTPA, DBTDPODPNA, DBTDPOTPA2 or DBTDPODPNA2; Described DBTDPOTPA structural formula is described DBTDPODPNA structural formula is described DBTDPOTPA2 structural formula is described DBTDPODPNA2 structural formula is
3. the synthetic method of a kind of dibenzothiophene base 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 dibenzothiophene base 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 dibenzothiophene base 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 dibenzothiophene base 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 dibenzothiophene base 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 the europium chloride aqueous solution are (1.2～1.5): 1.
8. the synthetic method of a kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group according to claim 2, is characterized in that the take amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part that triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine 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 dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group.
10. the application of a kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of modifying with triarylamine group as claimed in claim 1, is characterized in that a kind ofly usining the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex that triarylamine group modifies and applying in electroluminescent device as luminescent layer material.
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CN105037423A (en) * 2015-07-23 2015-11-11 北京大学 Effective rare earth complex luminescent material excited by shortwave ultraviolet

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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
CN102898473A (en) * 2012-11-02 2013-01-30 黑龙江大学 Multifunctional modified dibenzofuran-based di-phosphineoxy compound and preparation method and application thereof

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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
CN102898473A (en) * 2012-11-02 2013-01-30 黑龙江大学 Multifunctional modified dibenzofuran-based di-phosphineoxy compound and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037423A (en) * 2015-07-23 2015-11-11 北京大学 Effective rare earth complex luminescent material excited by shortwave ultraviolet
CN105037423B (en) * 2015-07-23 2017-12-12 北京大学 A kind of efficient rare-earth complexes luminous material of short wave ultraviolet excitation

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