CN109535168A - A kind of dioxin organic compound and its application - Google Patents

A kind of dioxin organic compound and its application Download PDF

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Publication number
CN109535168A
CN109535168A CN201811478654.XA CN201811478654A CN109535168A CN 109535168 A CN109535168 A CN 109535168A CN 201811478654 A CN201811478654 A CN 201811478654A CN 109535168 A CN109535168 A CN 109535168A
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layer
dioxin
organic compound
organic
compound
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储毅
柳佳欣
宋贺
胡晓腾
李燕藏
吴祜源
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JIUMU CHEMICAL PRODUCT CO Ltd YANTAI
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JIUMU CHEMICAL PRODUCT CO Ltd YANTAI
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Abstract

The invention discloses a kind of dioxin organic compound and its applications, the present invention is to contain the organic compound of dioxin as luminescent layer or electron transport layer materials, the OLED device of production, more existing OLED luminescent device, thermal stability, lower driving voltage and higher efficiency with higher, it lasts a long time, there is good industrialization prospect.

Description

A kind of dioxin organic compound and its application
Technical field
The present invention relates to organic photoelectrical material technical fields, more particularly, to a kind of using dioxin as the organic of center structure Compound-material and its application in OLED active display or illuminating device.
Background technique
Organic Light Emitting Diode (Organic Light Emitting Diode) abbreviation OLED display, comparative liquid crystal are aobvious Show device, OLED display is high with brightness, volume is thin, response is rapid, also there is low in energy consumption, performance to stablize, contrast height, width view The features such as angle, full color, wide operating temperature range, highlights very superior application prospect in display and lighting area.
OLED device mostly uses greatly " sandwich " structure.The structure is made of the different functional layer of multiple effects, is respectively Anode layer (usually tin indium oxide ITO), hole transmission layer (HTL), luminescent layer (EML), the electronics of transparent metal oxide pass Defeated layer (ETL) and metal cathode layer (usually low workfunction metal Li, Ca, Al, Mg, Ag etc.) are constituted.Yin-yang is pressed from both sides between the two poles of the earth Miscellaneous organic layer, radiant light are projected by the transparent conductive substrate of side.
Currently, for OLED luminescent device, mainly to the driving voltage of device, luminous efficiency, the performances such as service life into Row optimizing research.The performance for improving OLED device, other than device architecture and manufacture craft will be innovated, OLED luminous organic material Also it to constantly bring forth new ideas, develop the luminous material of OLED of the higher performances such as luminous efficiency height, luminescent layer good film-forming property, long service life Material is to adapt to.At present OLED luminous organic material luminous efficiency, in terms of be unable to satisfy wanting for device manufacturer It asks, it is particularly important to research and develop a kind of high performance OLED luminescent material.
Summary of the invention
In view of the above-mentioned problems, applicant provide a kind of preparation of dioxin organic compound and its in OLED photophore Application on part, organic compound of the present invention contain dioxin structure, have preferable stability of molecule.The OLED device prepared Part has superior photoelectric properties, and thermal stability, lower driving voltage and higher efficiency with higher, extending device makes With the service life, the requirement for meeting device manufacturer can be very good.
A kind of this dioxin organic compound, which is characterized in that the structural formula of the organic compound such as general formula (0) institute Show:
Wherein, Ar is expressed as substituted or unsubstituted C6-60 aryl, does not take containing one or more heteroatomic substitutions or The 5-60 unit's heteroaryl in generation；The hetero atom is nitrogen, oxygen or sulphur.
Further, the Ar is selected from one of following structural formula:
Specifically, the concrete structure formula of the organic compound is one of structural formula in following 52:
The present invention is also claimed comprising this triazine biphenyl bithiophene pyrimidines on OLED luminescent device Using:
A kind of organic electroluminescence device, it is characterised in that: organise comprising a kind of aforementioned any dioxin Close object.
Further, the organic electroluminescence device, including OLED display screen and OLED illumination.
Further, the organic electroluminescence device, including at least one layer of functional layer, the functional layer contain claim 1~3 any dioxin organic compound.
Further, the organic electroluminescence device, including electron transfer layer, the electron transfer layer contain claim 1~3 any dioxin organic compound.
Further, the organic electroluminescence device, including luminescent layer, it is any that the luminescent layer contains claims 1 to 3 The dioxin organic compound.
Compared with prior art, what the present invention was beneficial have the technical effect that the compounds of this invention using dioxin as skeleton, With carbazole and ring improves stability of material, and such compound is other than dioxin has biggish rigidity, with carbazole and ring It is one big pi bond conjugation rigid structure, steric hindrance is big, is not easy to rotate, so that the compounds of this invention material stereochemical structure is more Stablize.Applied to the thermal stability of OLED device in hole transmission layer, electron transfer layer or luminescent layer, can be improved, device is reduced Driving voltage, improve the efficiency of device, extend the service life of device, have good application effect and industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of organic electroluminescence device of the present invention.
Wherein, 1 is transparent substrate layer, and 2 be ITO, and 3 be hole injection layer, and 4 be hole transport/electronic barrier layer, and 5 be hair Photosphere, 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be cathode reflection electrode layer.
Specific embodiment
With reference to the accompanying drawings and examples, specific synthesis description is made to the organic compound being partially related in the present invention.
Embodiment 1: the synthesis of intermediate I
40.0g raw material A (278mmol) and 41.1g raw material B is added in the case where logical nitrogen in 500ml there-necked flask (278mmol) is added 76.7g K2CO3 (556mmol), 160mlDMF, is warming up to 130 DEG C~140 DEG C heat preservations, keeps the temperature 15h, TLC detects raw material end of reaction；It is cooled to room temperature, is filtered, filter cake is eluted with DMF, takes off dry solvent, with ethyl alcohol recrystallization, obtain 56g White intermediate A, yield 80%, purity 98.2%.The molar ratio of the raw material A and raw material B are 1:1, the raw material A with The molar ratio of K2CO3 is 1:2
56g compound intermediate A (222mmol), 74.2g raw material is added in the case where logical nitrogen in 1000ml there-necked flask 250ml toluene is added in C (444mmol) and 61.3gK2CO3 (444mmol), and 245g water, 2.56gPd (PPh3) 4 is added (2.22mmol) is warming up to 70~80 DEG C of heat preservations.TLC detects raw material end of reaction, is cooled to room temperature, and filters, and takes out filter cake, uses Water washing is primary, and filtering obtains 69.1g, yield 73%, purity 98.7% with re crystallization from toluene.
1000ml there-necked flask walks the intermediate B and 690ml o-dichlorohenzene of preparation in the case where logical nitrogen in addition, rise Temperature keeps the temperature 20h to 180 DEG C, and HPLC tracking reaction terminates (HPLC > 90%), is cooled to room temperature, filters, filtrate after reaction Silicagel column is crossed, column liquid vacuum rotary steam is crossed, is refining to obtain intermediate I 35.2g, yield 60%, HPLC:99.9% with toluene
LC-MS: intermediate I theoretical molecular weight is 362.1, and actually detected result molecular weight is 362.2.
H-NMR:δ10.3(2H,s),8.10(2H,d),7.80(2H,s),7.61(2H,d),7.51(2H,t),7.30 (2H,t),
7.01(2H,s)
The synthesis of 2 compound 1 of embodiment
The specific synthetic route of compound 1
Under nitrogen protection, 36.2g intermediate I (100mmol), 62.8g raw material D (400mmol), 38.4g are successively weighed Sodium tert-butoxide (400mmol), 0.92gPd2 (dba) 3 (1mmol), 0.4g tri-tert-butylphosphine (2mmol), are stirred with toluene, 100~110 DEG C are heated to, back flow reaction 12~24 hours, samples contact plate, display is remaining without intermediate 1, fully reacting；It is natural It being cooled to room temperature, filters, filtrate crosses silicagel column, crosses column liquid vacuum rotary steam to no fraction, and crude product gray solid is refined with toluene, Drying obtains 36g compound 1, yield: 70%, HPLC:99.9%
HPLC-MS: compound H theoretical molecular weight is 514.6, and actually detected result molecular weight is 514.2.
H-NMR:δ8.45(2H,d),7.94(2H,s),7.86(2H,d),7.56(4H,t),7.51(4H,d),7.46 (2H,d),7.38(2H,t),7.29(2H,t),7.01(2H,t)
The synthesis of 3 compound 8 of embodiment
The synthetic route of compound 8
Under nitrogen protection, 36.2g intermediate I (100mmol), 82.8g raw material E (400mmol), 38.4g are successively weighed Sodium tert-butoxide (400mmol), 0.92gPd2 (dba) 3 (1mmol), 0.4g tri-tert-butylphosphine (2mmol), are stirred with toluene, 100~110 DEG C are heated to, back flow reaction 12~24 hours, samples contact plate, display is without intermediate I residue, fully reacting；It is natural It is cooled to room temperature, filters, filtrate crosses silicagel column, crosses column liquid vacuum rotary steam to no fraction, is refined with toluene, it is solid that drying obtains white Body 39.9g compound 8, yield: 65%, HPLC:99.9%.
LC-MS: 8 theoretical molecular weight of compound is 614.7, and actually detected result molecular weight is 614.2.
H-NMR:δ8.45(2H,d),7.94(2H,s),7.86(2H,d),8.08(2H,d),8.07(2H,d),8.06 (2H,d),7.60(2H,d),7.55(2H,t),7.54(2H,t),7.53(2H,t),7.38(2H,t),7.29(2H,t),7.02 (2H,t)
The synthesis of 3 compound 13 of embodiment
The synthetic route of compound 13
Under nitrogen protection, 36.2g intermediate I (100mmol), 54.6g raw material F (200mmol), 38.4g are successively weighed Sodium tert-butoxide (400mmol), 0.92gPd2 (dba) 3 (1mmol), 0.4g tri-tert-butylphosphine (2mmol), are stirred with toluene, 100~110 DEG C are heated to, back flow reaction 12~24 hours, samples contact plate, display is without intermediate I residue, fully reacting；It is natural It is cooled to room temperature, filters, cross silicagel column, filtrate decompression is rotated to no fraction, refined with toluene, and drying obtains white solid 52.3g compound 13, yield: 70%, HPLC:99.9%.
LC-MS: 13 theoretical molecular weight of compound is 746.9, and actually detected result molecular weight is 746.3.
H-NMR:δ8.45(2H,d),7.94(2H,s),7.88(2H,d),7.87(2H,d),7.86(2H,d),7.38 (2H,t),7.34(2H,d),7.33(2H,s),7.29(2H,t),7.16(2H,d),7.15(2H,t),7.07(2H,t),7.02 (2H,t),1.72(12H,s)
The synthesis of 4 compound 32 of embodiment
The synthetic route of compound 32
Under nitrogen protection, 36.2g intermediate I (100mmol), 64.4g raw material G (200mmol), 38.4g are successively weighed Sodium tert-butoxide (400mmol), 0.92gPd2 (dba) 3 (1mmol), 0.4g tri-tert-butylphosphine (2mmol), are stirred with toluene, 100~110 DEG C are heated to, back flow reaction 12~24 hours, samples contact plate, display is without intermediate I residue, fully reacting；It is natural It is cooled to room temperature, filters, cross silicagel column, filtrate decompression is rotated to no fraction, refined with toluene, and drying obtains white solid 63.3g compound 32, yield: 75%, HPLC:99.9%.
LC-MS: 8 theoretical molecular weight of compound is 844.9, and actually detected result molecular weight is 844.3.
H-NMR:δ8.45(2H,d),8.12(2H,d),7.98(2H,s),7.94(2H,s),7.90(2H,d),7.86 (2H,d),7.63(2H,d),7.62(2H,d),7.58(2H,t),7.55(2H,t),7.50(2H,t),7.48(2H,d),7.46 (2H,d),7.45(2H,t),7.38(2H,t),7.29(2H,d),7.25(2H,t),7.02(2H,t)
The synthesis of 5 compound 47 of embodiment
The synthetic route of compound 47
Under nitrogen protection, 36.2g intermediate I (100mmol), 53.5g raw material H (200mmol), 38.4g are successively weighed Sodium tert-butoxide (400mmol), 0.92gPd2 (dba) 3 (1mmol), 0.4g tri-tert-butylphosphine (2mmol), are stirred with toluene, 100~110 DEG C are heated to, back flow reaction 12~24 hours, samples contact plate, display is without intermediate I residue, fully reacting；It is natural It is cooled to room temperature, filters, cross silicagel column, filtrate decompression is rotated to no fraction, and crude product gray solid is refined with toluene, dried To 57.8g compound 47, yield: 70%, HPLC:99.9%.
LC-MS: 8 theoretical molecular weight of compound is 824.9, and actually detected result molecular weight is 824.3.
H-NMR:δ8.45(2H,d),8.28(8H,d),7.94(2H,s),7.86(2H,d),7.50(8H,t),7.40 (4H,d),7.38(2H,t),7.29(2H,t),7.02(2H,t)
Below by comparative example 1 and Examples 1 to 5 compound the answering in OLED device that the present invention will be described in detail synthesizes Use effect.
Comparative example 1
Device comparative example 1: as shown in Figure 1, a kind of electroluminescent device, preparation step includes: a) to clean transparent substrate Ito anode layer 2 on layer 1, is cleaned each 15 minutes respectively with deionized water, acetone, EtOH Sonicate, then in plasma clean It is handled 2 minutes in device；B) on ito anode layer 2, hole injection layer material HAT-CN, thickness are deposited by vacuum evaporation mode For 10nm, this layer is as hole injection layer 3；C) on hole injection layer 3, hole mobile material is deposited by vacuum evaporation mode TPD, with a thickness of 60nm, which is hole transmission layer 4；D) luminescent layer 5 is deposited on hole transmission layer 4, based on CBP Material, Ir (ppy) 3 are dopant, and the mass ratio of Ir (ppy) 3 and CBP are 10:90, with a thickness of 30nm；E) luminescent layer 5 it On, electron transport material TPBI is deposited by vacuum evaporation mode, with a thickness of 40nm, this layer of organic material is as electron transfer layer 6 use；F) on electron transfer layer 6, by vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electron injection Layer 7；G) on electron injecting layer 7, vacuum evaporation cathode Al (100nm), the layer is cathode reflection electrode layer 8；According to above-mentioned After step completes the production of electroluminescent device, the luminous efficiency of measurement device and service life, the result is shown in shown in table 2.Related material The molecular structural formula of material is as follows:
The manufacture craft of the device compared with device comparative example 1 of device embodiments 1~5 of the present invention is identical, And identical baseplate material and electrode material are used, the film thickness of electrode material is also consistent, except that device Examples 1 to 3 is use material of the present invention as luminescent layer material of main part, with the ratio of dopant Ir (ppy) 3 and than It is consistent compared with example 1；Electron transport layer materials in 4~5 pairs of devices of device embodiments convert.Used in each principal structural layer of device Compound such as table 1, the performance test results of each embodiment obtained device are as shown in table 2.
Table 1
Luminous organic material prepared by the present invention, using KEITHELY2400 type source measuring unit, MINOLTA CS- 1000A spectrophotometric test meter detection, to evaluate efficiency (under the current density of 10mA/cm2) and the longevity of each organic luminescent device Order (T90 under the current density of 10mA/cm2) and color.The stream when brightness of service life finger device part drops to the 90% of original intensity The time quantum to die.As a result it see the table below
Table 2
As can be seen from Table 2, example has better characteristics than comparing exemplary organic luminescent device.(such as it is increased Efficiency and extended service life)
From the point of view of above data application, dioxin organic electroluminescent compounds of the present invention are in OLED luminescent device In have good application effect, have good industrialization prospect.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of dioxin organic compound, which is characterized in that shown in the structural formula of the organic compound such as general formula (0):
Wherein, Ar is expressed as substituted or unsubstituted C6-60Aryl contains one or more heteroatomic substituted or unsubstituted 5- 60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur.
2. a kind of dioxin organic compound according to claim 1, which is characterized in that the Ar is selected from such as flowering structure One of formula:
3. a kind of dioxin organic compound according to claim 1, which is characterized in that the tool of the organic compound Body structural formula is one of following structural formula:
4. a kind of any dioxin organic compound of claim 1-3 is preparing answering for organic electroluminescence device With.
5. a kind of organic electroluminescence device, including at least one layer of functional layer, which is characterized in that the functional layer, which contains, has the right to want Seek 1~3 described in any item dioxin organic compounds.
6. a kind of organic electroluminescence device, including electron transfer layer, which is characterized in that the electron transport layer materials are right It is required that 1~3 described in any item dioxin organic compounds.
7. a kind of organic electroluminescence device, including luminescent layer, which is characterized in that the luminescent layer, which contains claims 1 to 3, appoints Dioxin organic compound described in one.
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CN108203416A (en) * 2016-12-20 2018-06-26 江苏三月光电科技有限公司 Using fluorenes as the compound and organic electroluminescence device of core
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KR20130110051A (en) * 2012-03-27 2013-10-08 에스에프씨 주식회사 Carbazole derivatives and organoelectro luminescent device using the same
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