CN103980302B - A kind of with the application of the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification - Google Patents
A kind of with the application of the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification Download PDFInfo
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Abstract
With an application for the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification, it relates to a kind of application of europium complex.The object of the invention is to solve existing rare earth compounding and there is chemical stability and cavity transmission ability is poor, rare earth compounding is applied in electroluminescent device to be existed easily and material of main part is separated, the problem that luminous efficiency is low.Structure is:
Description
Technical field
The present invention relates to a kind of application of europium complex.
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 EL display.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 of full color flat-panel displays part middle ideal, 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 the advantage of good monochromaticity, be widely used in preparing electroluminescent device, but up to the present, as the organic coordination compound of electroluminescent rare earth organic complex mainly europium, terbium, and rare-earth organic electroluminescence device in performance far from and other is using small molecule material and polymer materials as the El element of luminescent layer, this is because: chemical stability and the fluorescent stability of rare earth compounding are poor, can not make high-quality film; Device light emitting efficiency is low, and most of electric energy conversion is heat energy etc.; Often there is sharp base composed emission in rare earth electroluminescent device, severe jamming Line Emission; Device lifetime is short.
Therefore, existing rare earth compounding there is chemical stability and cavity transmission ability is poor, and rare earth compounding is applied in electroluminescent device to be existed 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 and there is chemical stability and cavity transmission ability is poor, rare earth compounding is applied in electroluminescent device to be existed easily and material of main part is separated, the problem that luminous efficiency is low, and provide a kind of with the application of the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification.
A kind of neutral ligand of being formed by the derivative of dibenzothiophene base bidentate aromatic phosphines oxygen with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification and beta-diketonate ligand complexing europium ion are formed, 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 with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification is carried 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 one and the volume ratio of dehydrated alcohol are (0.1mmol ~ 0.2mmol): 1mL;
Two, six trichloride hydrate europiums are dissolved in distilled water, obtain the europium chloride aqueous solution;
The amount of substance of six trichloride hydrate europiums 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 with triaryl amine base group modification is dissolved in methylene dichloride, obtains the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution with triaryl amine base group modification;
Described in step 3 with the volume ratio of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and methylene dichloride for 1mmol:(30mL ~ 40mL);
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, rate of titration be 5/condition of min ~ 10 droplet/min under the aqueous sodium hydroxide solution of 12mol/L ~ 15mol/L is added drop-wise in container, be the 1h ~ 3h that refluxes under the condition of 60 DEG C ~ 70 DEG C in temperature, then by the europium chloride aqueous solution to be added drop-wise in container under the rate of titration of 5/min ~ 10 droplet/min, be the 1h ~ 3h that refluxes under the condition of 60 DEG C ~ 70 DEG C in temperature, with the rate of titration of 5/min ~ 10 droplet/min, the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution with triaryl amine base group modification is added drop-wise in container again, be back flow reaction 12h ~ 18h under the condition of 60 DEG C ~ 70 DEG C in temperature, re-use Rotary Evaporators alcohol solvent is steamed, 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 of the 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 ~ 1.5): 1;
Described in step 4 with in the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of triaryl amine base group modification with the amount of substance of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and beta-diketon in beta-diketon/dehydrated alcohol mixing solutions than for 1:3;
Five, powdery precipitate is used distilled water filtering and washing 2 times ~ 3 times, re-use dehydrated alcohol filtering and washing 2 times ~ 3 times, be dry 6h ~ 8h under the condition of 60 DEG C ~ 70 DEG C again in temperature, obtain the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex with triaryl amine base group modification;
Described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for 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
Apply in electroluminescent device using the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification as emitting layer material.
Advantage of the present invention: one, material of main part and guest materials are combined, improves the energy transfer efficiency between molecule, and conjugated system adds steric effect more greatly simultaneously, reduces the self quenching of triplet excitons;
Two, when the present invention is used for electroluminescent device, the introducing of cavity transmission group can the transmission of equilbrium carrier, improves luminous efficiency, thus obtains the europium photoelectric functional material that a class has wide application prospect.
The present invention can obtain a kind of with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification.
Accompanying drawing explanation
Fig. 1 is the Eu (DBM) that test one is synthesized
3(DBTDPOTPA) Ultraluminescence spectrum; In Fig. 1-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
Fig. 2 is the Eu (TTA) that test three is synthesized
3(DBTDPOTPA) Ultraluminescence spectrum; In Fig. 2-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
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 fluorescence emission spectra curve;
Fig. 4 is the Eu (TTA) that test seven is synthesized
3(DBTDPODPNA) Ultraluminescence spectrum; In Fig. 4-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
Fig. 5 is the Eu (DBM) that test nine is synthesized
3(DBTDPOTPA2) Ultraluminescence spectrum; In Fig. 5-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
Fig. 6 is the Eu (TTA) that test 11 is synthesized
3(DBTDPOTPA2) Ultraluminescence spectrum; In Fig. 6-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
Fig. 7 is the Eu (DBM) that test 13 is synthesized
3(DBTDPODPNA2) Ultraluminescence spectrum; In Fig. 7-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
Fig. 8 is the Eu (TTA) that test ten pentahapto becomes
3(DBTDPODPNA2) Ultraluminescence spectrum; In Fig. 8-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve;
Fig. 9 is the Eu (DBM) that test one is synthesized
3(DBTDPOTPA) infrared spectrogram;
Figure 10 is the Eu (TTA) that test three is synthesized
3(DBTDPOTPA) infrared spectrogram;
Figure 11 is the Eu (DBM) that test pentahapto becomes
3(DBTDPODPNA) infrared spectrogram;
Figure 12 is the Eu (TTA) that test seven is synthesized
3(DBTDPODPNA) infrared spectrogram;
Figure 13 is the Eu (DBM) that test nine is synthesized
3(DBTDPOTPA2) infrared spectrogram;
Figure 14 is the Eu (TTA) that test 11 is synthesized
3(DBTDPOTPA2) infrared spectrogram;
Figure 15 is the Eu (DBM) that test 13 is synthesized
3(DBTDPODPNA2) infrared spectrogram;
Figure 16 is the Eu (TTA) that test ten pentahapto becomes
3(DBTDPODPNA2) infrared spectrogram;
Figure 17 is the Eu (DBM) of test two use-testing one synthesis
3(DBTDPOTPA) as the electroluminescent device J-V-B curve of the emitting layer material of electroluminescent device; In Figure 17-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 18 is the Eu (TTA) of test four use-testing three synthesis
3(DBTDPOTPA) as the electroluminescent device J-V-B curve of the emitting 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 pentahapto becomes
3(DBTDPODPNA) as the electroluminescent device J-V-B curve of the emitting layer material of electroluminescent device; In Figure 19-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 20 is the Eu (TTA) of test eight use-testing seven synthesis
3(DBTDPODPNA) as the electroluminescent device J-V-B curve of the emitting layer material of electroluminescent device; In Figure 20-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 21 is the Eu (DBM) of test ten use-testing nine synthesis
3(DBTDPOTPA2) as the electroluminescent device J-V-B curve of the emitting layer material of electroluminescent device; In Figure 21-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 22 is the Eu (TTA) of test 12 use-testing 11 synthesis
3(DBTDPOTPA2) as the electroluminescent device J-V-B curve of the emitting layer material of electroluminescent device; In Figure 22-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 23 is the Eu (DBM) of test 14 use-testing 13 synthesis
3(DBTDPODPNA2) as the electroluminescent device J-V-B curve of the emitting 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 pentahapto becomes
3(DBTDPODPNA2) as the electroluminescent device J-V-B curve of the emitting layer material of electroluminescent device; In Figure 24-and-be current density voltage curve ,-■-be brightness-voltage curve;
Figure 25 is the Eu (DBM) of test two use-testing one synthesis
3(DBTDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 26 is the Eu (TTA) of test four use-testing three synthesis
3(DBTDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 27 is the Eu (DBM) that test six use-testing pentahapto becomes
3(DBTDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 28 is the Eu (TTA) of test eight use-testing seven synthesis
3(DBTDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 29 is the Eu (DBM) of test ten use-testing nine synthesis
3(DBTDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 30 is the Eu (TTA) of test 12 use-testing 11 synthesis
3(DBTDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 31 is the Eu (DBM) of test 14 use-testing 13 synthesis
3(DBTDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device;
Figure 32 is the Eu (TTA) that test 16 use-testing ten pentahapto becomes
3(DBTDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.
Embodiment
Embodiment one: present embodiment is that a kind of neutral ligand of being formed by the derivative of dibenzothiophene base bidentate aromatic phosphines oxygen with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification and beta-diketonate ligand complexing europium ion are formed, 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, improves the energy transfer efficiency between molecule, and conjugated system adds steric effect more greatly simultaneously, reduces the self quenching of triplet excitons;
Two, when present embodiment is used for electroluminescent device, the introducing of cavity transmission group can the transmission of equilbrium carrier, improves luminous efficiency, thus obtains the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification.
Embodiment two: present embodiment is a kind of synthetic method with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification is 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 one and the volume ratio of dehydrated alcohol are (0.1mmol ~ 0.2mmol): 1mL;
Two, six trichloride hydrate europiums are dissolved in distilled water, obtain the europium chloride aqueous solution;
The amount of substance of six trichloride hydrate europiums 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 with triaryl amine base group modification is dissolved in methylene dichloride, obtains the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution with triaryl amine base group modification;
Described in step 3 with the volume ratio of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and methylene dichloride for 1mmol:(30mL ~ 40mL);
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, rate of titration be 5/condition of min ~ 10 droplet/min under the aqueous sodium hydroxide solution of 12mol/L ~ 15mol/L is added drop-wise in container, be the 1h ~ 3h that refluxes under the condition of 60 DEG C ~ 70 DEG C in temperature, then by the europium chloride aqueous solution to be added drop-wise in container under the rate of titration of 5/min ~ 10 droplet/min, be the 1h ~ 3h that refluxes under the condition of 60 DEG C ~ 70 DEG C in temperature, with the rate of titration of 5/min ~ 10 droplet/min, the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution with triaryl amine base group modification is added drop-wise in container again, be back flow reaction 12h ~ 18h under the condition of 60 DEG C ~ 70 DEG C in temperature, re-use Rotary Evaporators alcohol solvent is steamed, 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 of the 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 ~ 1.5): 1;
Described in step 4 with in the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of triaryl amine base group modification with the amount of substance of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and beta-diketon in beta-diketon/dehydrated alcohol mixing solutions than for 1:3;
Five, powdery precipitate is used distilled water filtering and washing 2 times ~ 3 times, re-use dehydrated alcohol filtering and washing 2 times ~ 3 times, be dry 6h ~ 8h under the condition of 60 DEG C ~ 70 DEG C again in temperature, obtain the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex with triaryl amine base group modification;
Described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for 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, improves the energy transfer efficiency between molecule, and conjugated system adds steric effect more greatly simultaneously, reduces the self quenching of triplet excitons;
Two, when present embodiment is used for electroluminescent device, the introducing of cavity transmission group can the transmission of equilbrium carrier, improves luminous efficiency, thus obtains the europium photoelectric functional material that a class has wide application prospect.
Present embodiment can obtain a kind of with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification.
Embodiment three: present embodiment and embodiment two difference are: the beta-diketon described in step one is phenylbenzene methyl ethyl diketone or thienyl trifluoromethyl methyl ethyl diketone.Other steps are identical with embodiment two.
Embodiment four: one of present embodiment and embodiment two or three difference is: the amount of substance of the beta-diketon described in step one 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: the amount of substance of six trichloride hydrate europiums 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 of the 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.Other steps are identical with embodiment two to six.
Embodiment eight: one of present embodiment and embodiment two to seven difference is: described in step 3 with the volume ratio of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and methylene dichloride for 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 distilled water filtering and washing 2 times ~ 3 times, re-use dehydrated alcohol filtering and washing 2 times ~ 3 times, be dry 7h ~ 8h under the condition of 65 DEG C ~ 70 DEG C again in temperature, obtain the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex with triaryl amine base group modification.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 using triaryl amine base group modification is applied in electroluminescent device as emitting layer material.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of Eu (DBM)
3(DBTDPOTPA) with the synthetic method of the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification, be 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 one and the volume ratio of dehydrated alcohol are 0.1mmol:1mL;
Two, six trichloride hydrate europiums are dissolved in distilled water, obtain the europium chloride aqueous solution;
The amount of substance of six trichloride hydrate europiums described in step 2 and the volume ratio of distilled water are 1mmol:1mL;
Three, the dibenzothiophene base bidentate aromatic phosphines oxygen part with triaryl amine base group modification is dissolved in methylene dichloride, obtains the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution with triaryl amine base group modification;
Described in step 3 with the volume ratio of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and methylene dichloride for 1mmol:30mL;
Four, beta-diketon/dehydrated alcohol mixing solutions is joined in container, be under the condition of 5/min, the aqueous sodium hydroxide solution of 12mol/L is added drop-wise in container in rate of titration, be the 1h that refluxes under the condition of 70 DEG C in temperature, then by the europium chloride aqueous solution to be added drop-wise in container under the rate of titration of 5/min, be the 1h that refluxes under the condition of 70 DEG C in temperature, with the rate of titration of 5/min, the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution with triaryl amine base group modification is added drop-wise in container again, be back flow reaction 12h under the condition of 70 DEG C in temperature, re-use Rotary Evaporators alcohol solvent is steamed, 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 of the aqueous sodium hydroxide solution of the 12mol/L described in step 4 and the volume ratio of the europium chloride aqueous solution are 1:1;
Described in step 4 with in the dibenzothiophene base bidentate aromatic phosphines oxygen part/dichloromethane solution of triaryl amine base group modification with the amount of substance of the amount of substance of the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification and beta-diketon in beta-diketon/dehydrated alcohol mixing solutions than for 1:3;
Five, powdery precipitate is used distilled water filtering and washing 3 times, re-use dehydrated alcohol filtering and washing 3 times, then be dry 8h under the condition of 70 DEG C in temperature, obtaining structural formula is
with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA).
Beta-diketon described in step one is phenylbenzene methyl ethyl diketone;
Described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPOTPA, described DBTDPOTPA structural formula is
described in step 4 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPOTPA according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of test one is as follows:
Use elemental analyser to test one synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 test one synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA) test, as shown in Figure 1, Fig. 1 is the Eu (DBM) that test one is synthesized
3(DBTDPOTPA) Ultraluminescence spectrum; In Fig. 1-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 1, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test one synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1~ 370cm
-1, as shown in Figure 9, Fig. 9 is the Eu (DBM) that test one is synthesized
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: at tin indium oxide ITO as coating the hole transmission layer that a layer thickness is 60nm between anode and luminescent layer, Ca is electron injecting layer, electrode materials is aluminium, and the electron injecting layer of electrode materials adopts vacuum evaporation technology film, and hole transmission layer and luminescent layer adopt spin coating technique film.The structure of device is: ITO/PEDTO/PSS (60nm)/PVK:PBD: with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex (65:30:5 of triaryl amine base group modification; 60nm)/Ca (25nm)/Al (100nm);
Test the luminescent layer described in two be test one synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA), the dopant material of PVK and PBD; Test the luminescent layer described in two in test one synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 of test described in two is 60nm; The electron injecting layer of the electrode materials of test described in two adopts vacuum evaporation technology film, and hole transmission layer and luminescent layer adopt spin coating technique film;
The PEDTO/PSS of test described in two is poly-3,4-ethylene dioxythiophene/poly styrene sulfonate;
The PVK of test described in two is Polyvinyl carbazole;
The PBD of test described in two is 2-(4'-trimethylphenylmethane base)-5-(4'-xenyl)-1,3,4-oxadiazoles.
Use PR650 and Keithley2400 instrument to test a synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA) electroluminescent device made as emitting layer material is tested, and as shown in figure 17, Figure 17 is the Eu (DBM) of test two use-testing one synthesis
3(DBTDPOTPA) as the electroluminescent device J-V-B curve of the emitting 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 Eu (DBM) of test two use-testing one synthesis
3(DBTDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device, as can be seen from Figure 25,612nm place is the characteristic emission peak of Eu.
Test three: this test with test one difference is: the beta-diketon described in step one is thienyl trifluoromethyl methyl ethyl diketone.Other step and parameter identical with test one.
Test three synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA) structural formula is
The reaction formula of this test is as follows:
Use elemental analyser to test three synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 the observed value of reality: 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 test three synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA) test, as shown in Figure 2, Fig. 2 is the Eu (TTA) that test three is synthesized
3(DBTDPOTPA) Ultraluminescence spectrum; In Fig. 2-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 2, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test three synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1~ 370cm
-1, as shown in Figure 10, Figure 10 is the Eu (TTA) that test three is synthesized
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 be: the luminescent layer described in this test be test three synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA), the dopant material of PVK and PBD; In described luminescent layer test three synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 identical with test two.
Use PR650 and Keithley2400 instrument to test three synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA) electroluminescent device made as luminescent layer raw material is tested, and as shown in figure 18, Figure 18 is the Eu (TTA) of test four use-testing three synthesis
3(DBTDPOTPA) as the electroluminescent device J-V-B curve of the emitting 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 Eu (TTA) of test four use-testing three synthesis
3(DBTDPOTPA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 26,612nm place is the characteristic emission peak of Eu.
Test five: this test with test a difference be: described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA; Described DBTDPODPNA structural formula is
other step and parameter identical with test one.
Test pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA) structural formula is
described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to test pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 the observed value of reality: C is 72.89; H is 4.34; Eu is 9.12; N is 0.97; O is 7.57; S is 1.74.
Use ultraviolet-visible pectrophotometer and spectrograph to test pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 fluorescence emission spectra curve.As can be seen from Figure 3, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 and be: the luminescent layer described in this test be test that pentahapto becomes with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA), the dopant material of PVK and PBD; Test in described luminescent layer pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 identical with test two.
Use PR650 with Keithley2400 instrument to test that pentahapto becomes with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA) electroluminescent device made as luminescent layer raw material is tested, and as shown in figure 19, Figure 19 is the Eu (DBM) that test six use-testing pentahapto becomes
3(DBTDPODPNA) as the electroluminescent device J-V-B curve of the emitting 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 pentahapto becomes
3(DBTDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 27,612nm place is the characteristic emission peak of Eu.
Test seven: this test with test one difference is: the beta-diketon described in step one is thienyl trifluoromethyl methyl ethyl diketone; Described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA; Described DBTDPODPNA structural formula is
other step and parameter identical with test one.
Test seven synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA) structural formula is
described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to test seven synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 the observed value of reality: 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 test seven synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA) test, as shown in Figure 4, Fig. 4 is the Eu (TTA) that test seven is synthesized
3(DBTDPODPNA) Ultraluminescence spectrum; In Fig. 4-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 4, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test seven synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA) measure, adopt KBr pressed disc method, test specification is 4000cm
-1~ 370cm
-1, as shown in figure 12, Figure 12 is the Eu (TTA) that test seven is synthesized
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 be: the luminescent layer described in this test be test seven synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA), the dopant material of PVK and PBD; In described luminescent layer test seven synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 identical with test two.
Use PR650 and Keithley2400 instrument to test seven synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA) electroluminescent device made as luminescent layer raw material is tested, and as shown in figure 20, Figure 20 is the Eu (TTA) of test eight use-testing seven synthesis
3(DBTDPODPNA) as the electroluminescent device J-V-B curve of the emitting 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 Eu (TTA) of test eight use-testing seven synthesis
3(DBTDPODPNA) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 28,612nm place is the characteristic emission peak of Eu.
Test nine: this test with test a difference be: described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPOTPA2; Described DBTDPOTPA2 structural formula is
other step and parameter identical with test one.
Test nine synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA2) structural formula is
described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPOTPA2 according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to test nine synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 the observed value of reality: 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 test nine synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA2) test, as shown in Figure 5, Fig. 5 is the Eu (DBM) that test nine is synthesized
3(DBTDPOTPA2) Ultraluminescence spectrum; In Fig. 5-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 5, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test nine synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA2) measure, adopt KBr pressed disc method, test specification is 4000cm
-1~ 370cm
-1, as shown in figure 13, Figure 13 is the Eu (DBM) that test nine is synthesized
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 be: the luminescent layer described in this test be test nine synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA2), the dopant material of PVK and PBD; In described luminescent layer test nine synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 identical with test two.
Use PR650 and Keithley2400 instrument to test nine synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPOTPA2) electroluminescent device made as luminescent layer raw material is tested, and as shown in figure 21, Figure 21 is the Eu (DBM) of test ten use-testing nine synthesis
3(DBTDPOTPA2) as the electroluminescent device J-V-B curve of the emitting 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 Eu (DBM) of test ten use-testing nine synthesis
3(DBTDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 29,612nm place is the characteristic emission peak of Eu.
Test 11: this test with test one difference is: the beta-diketon described in step one is thienyl trifluoromethyl methyl ethyl diketone; Described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPOTPA2; Described DBTDPOTPA2 structural formula is
other step and parameter identical with test one.
Test 11 synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA2) structural formula is
described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPOTPA2 according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to test 11 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 the observed value of reality: 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 test 11 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA2) test, as shown in Figure 6, Fig. 6 is the Eu (TTA) that test 11 is synthesized
3(DBTDPOTPA2) Ultraluminescence spectrum; In Fig. 6-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 6, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test 11 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA2) measure, adopt KBr pressed disc method, test specification is 4000cm
-1~ 370cm
-1, as shown in figure 14, Figure 14 is the Eu (TTA) that test 11 is synthesized
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 be: the luminescent layer described in this test be test 11 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA2), the dopant material of PVK and PBD; In described luminescent layer test 11 synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 identical with test two.
Use PR650 and Keithley2400 instrument to test 11 synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPOTPA2) electroluminescent device made as luminescent layer raw material is tested, and as shown in figure 22, Figure 22 is the Eu (TTA) of test 12 use-testing 11 synthesis
3(DBTDPOTPA2) as the electroluminescent device J-V-B curve of the emitting 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 Eu (TTA) of test 12 use-testing 11 synthesis
3(DBTDPOTPA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 30,612nm place is the characteristic emission peak of Eu.
Test 13: this test with test one difference be: described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA2; Described DBTDPODPNA2 structural formula is
other step and parameter identical with test one.
Test 13 synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA2) structural formula is
described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA2 according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to test 13 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 the observed value of reality: 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 test 13 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA2) test, as shown in Figure 7, Fig. 7 is the Eu (DBM) that test 13 is synthesized
3(DBTDPODPNA2) Ultraluminescence spectrum; In Fig. 7-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 7, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test 13 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA2) measure, adopt KBr pressed disc method, test specification is 4000cm
-1~ 370cm
-1, as shown in figure 15, Figure 15 is the Eu (DBM) that test 13 is synthesized
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 be: the luminescent layer described in this test be test 13 synthesize with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA2), the dopant material of PVK and PBD; In described luminescent layer test 13 synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
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 identical with test two.
Use PR650 and Keithley2400 instrument to test 13 synthesis with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (DBM) of triaryl amine base group modification
3(DBTDPODPNA2) electroluminescent device made as luminescent layer raw material is tested, and as shown in figure 23, Figure 23 is the Eu (DBM) of test 14 use-testing 13 synthesis
3(DBTDPODPNA2) as the electroluminescent device J-V-B curve of the emitting 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 Eu (DBM) of test 14 use-testing 13 synthesis
3(DBTDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 31,612nm place is the characteristic emission peak of Eu.
Test 15: this test with test one difference is: the beta-diketon described in step one is thienyl trifluoromethyl methyl ethyl diketone; Described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA2; Described DBTDPODPNA2 structural formula is
other step and parameter identical with test one.
Test ten pentahaptos become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA2) structural formula is
described in step 3 with the dibenzothiophene base bidentate aromatic phosphines oxygen part of triaryl amine base group modification for DBTDPODPNA2 according to public announcement of a patent application number is: CN102898473A is prepared from;
The reaction formula of this test is as follows:
Use elemental analyser to test ten pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 the observed value of reality: C is 62.78; H is 3.45; Eu is 7.44; N is 1.56; O is 6.38; S is 6.34.
Use ultraviolet-visible pectrophotometer and spectrograph to test ten pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA2) test, as shown in Figure 8, Fig. 8 is the Eu (TTA) that test ten pentahapto becomes
3(DBTDPODPNA2) Ultraluminescence spectrum; In Fig. 8-and ■-be ultra-violet absorption spectrum curve ,--be fluorescence emission spectra curve.As can be seen from Figure 8, the characteristic emission peak of europium ion is had at 612nm place.
Use Perkin-Elmer60000 infrared spectrometer to test ten pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 pentahapto becomes
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 be: the luminescent layer described in this test be test ten pentahapto become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA2), the dopant material of PVK and PBD; Test in described luminescent layer ten pentahaptos become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
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 identical with test two.
Use PR650 with Keithley2400 instrument to test that ten pentahaptos become with dibenzothiophene base bidentate aromatic phosphines oxygen europium complex Eu (TTA) of triaryl amine base group modification
3(DBTDPODPNA2) electroluminescent device made 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 pentahapto becomes
3(DBTDPODPNA2) as the electroluminescent device J-V-B curve of the emitting 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 pentahapto becomes
3(DBTDPODPNA2) as the electroluminescent spectrogram of the electroluminescent device of the emitting layer material of electroluminescent device.As can be seen from Figure 32,612nm place is the characteristic emission peak of Eu.
Claims (1)
1., with an application for the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification, it is characterized in that a kind of dibenzothiophene base bidentate aromatic phosphines oxygen europium complex using triaryl amine base group modification is applied in electroluminescent device as emitting layer material;
Described a kind of neutral ligand of being formed by the derivative of dibenzothiophene base bidentate aromatic phosphines oxygen with the dibenzothiophene base bidentate aromatic phosphines oxygen europium complex of triaryl amine base group modification and beta-diketonate ligand complexing europium ion are formed, and structure is:
wherein, described Ar
1during for H, Ar
2for
or Ar
1for
and Ar
1with Ar
2structural formula identical;
Described R
1during for phenyl, R
2for phenyl;
Described R
1for CF
3time, R
2for α-thienyl.
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| 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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