CN105153031B - A kind of electroluminescent organic material and its preparation method and application - Google Patents

A kind of electroluminescent organic material and its preparation method and application Download PDF

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CN105153031B
CN105153031B CN201510499970.5A CN201510499970A CN105153031B CN 105153031 B CN105153031 B CN 105153031B CN 201510499970 A CN201510499970 A CN 201510499970A CN 105153031 B CN105153031 B CN 105153031B
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CN105153031A (en
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尹恩心
赵明
刘成凯
秦翠英
王钊
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Jilin Optical and Electronic Materials Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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    • C07—ORGANIC CHEMISTRY
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

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Abstract

The present invention proposes a kind of organic compound, it is with being imported with the spiro structure of structural rigidity and high thermal stability in the design of chemical constitution by the acridine functional group with high electron hole efficiency of transmission, excellent tri-arylamine group and excellent electron transport material 9 with hole transport performance, 9 dimethyl fluorenes combine, it is high to form a kind of thermal stability, the excellent compound of luminous efficiency, the introducing of different substituents, electron transition can be changed, adjust its luminous peak position, the device being fabricated to the material of the present invention disclosure satisfy that the demand of industrialized production.

Description

A kind of electroluminescent organic material and its preparation method and application
Technical field
It is more particularly to a kind of as master the present invention relates to a kind of organic compound and the Organnic electroluminescent device for including it The organic compound of body material and the phosphorescent organic electroluminescent device for including it.
Background technology
Organnic electroluminescent device (organic electroluminescent device), also referred to as organic light emission two Pole pipe (organic light-emitting diode；OLED), it is a kind of light emitting diode using organic layer as active layers (LED).Because Organnic electroluminescent device has low voltage operating, high brightness, in light weight, wide viewing angle and high reduced value etc. Advantage, it has been used in gradually in recent years on flat panel display (flat panel display).It is different from liquid crystal display, The organic LED pixels array that display of organic electroluminescence is included is that have self luminous characteristic, therefore is not required to outer Add backlight.
In general, Organic Light Emitting Diode component includes a pair of electrodes, and organic light emission Jie between the electrodes Matter layer.Luminous is inducement in following phenomenon.When electric field imposes on two electrodes, negative electrode injection electronics to organic light emitting medium layer, Anode projects hole to organic light emitting medium layer.When electronics and hole combine in organic light emitting medium layer, exciton can be produced (excitons).Electronics and hole in conjunction with just along with luminous.
According to the spin state (spin state) of hole and electronics, by hole and electronics in conjunction with and caused exciton can Spin state with triplet (triplet) or singlet state (singlet).By singlet excitons (singlet exciton) institute It is caused to light as fluorescence (fluorescence), and lighted as caused by triplet exciton (triplet exciton) and be Phosphorescence (phosphorescence).The luminous efficiency of phosphorescence is three times of fluorescence.Therefore, develop efficient phosphor material with The luminous efficiency for promoting Organic Light Emitting Diode component is very important.
The content of the invention
The present invention proposes a kind of organic compound, its be by the acridine functional group with high electron hole efficiency of transmission with Imported with the spiro structure of structural rigidity and high thermal stability in the design of chemical constitution, excellent with hole transport performance three Arylamine class and excellent electron transport material 9, the combination of 9- dimethyl fluorenes form a kind of thermal stability height, and luminous efficiency is excellent Different compound.
It is a further object to provide a kind of preparation method of high efficiency organic electroluminescence material.
To achieve the above object, the present invention provides a kind of efficient electroluminescent organic material, it is characterised in that structure is led to Formula such as formula（1）It is shown：
Formula（1）；
Wherein, R1For hydrogen, halogen, cyano group, C1 ~ C30 alkyl, C6 ~ C50 aryl, C7 ~ C50 aralkyl or C5 ~ C50 heteroaryl；
R2For hydrogen, halogen, cyano group, C1 ~ C30 alkyl, C6 ~ C50 aryl, C7 ~ C50 aralkyl, C7 ~ C50 virtue Base alkoxy, C7 ~ C50 aryl alkane sulfydryl or C5 ~ C50 heteroaryl.
Wherein, the alkyl be straight chained alkyl, branched alkyl, cycloalkyl, at least one substituent substitution direct-connected alkyl, The branched alkyl of at least one substituent substitution or the cycloalkyl of at least one substituent substitution；Wherein, the substituent independence One or more in halogen, cyano group, hydroxyl and sulfydryl.
The aryl is preferably unsubstituted aryl or the aryl of at least one substituent substitution；Wherein, the substituent is only Vertical selection halogen, amino, cyano group, nitro, hydroxyl or sulfydryl；
The aryl alkyl is preferably unsubstituted aryl alkyl or the aryl alkyl of at least one substituent substitution；Wherein, Selection halogen, amino, cyano group, nitro, hydroxyl or the sulfydryl of the substituent independence；
The alkoxy aryl is preferably unsubstituted alkoxy aryl or the arylalkoxy of at least one substituent substitution Base；Wherein, selection halogen, amino, cyano group, nitro, hydroxyl or the sulfydryl of the substituent independence；
The aryl alkane sulfydryl is preferably the aryl alkane mercapto of unsubstituted aryl alkane sulfydryl or at least one substituent substitution Base；Wherein, selection halogen, amino, cyano group, nitro, hydroxyl or the sulfydryl of the substituent independence；
The heteroaryl is preferably unsubstituted heteroaryl or the heteroaryl of at least one substituent substitution；Wherein, heteroaryl In hetero atom be nitrogen, sulphur or oxygen；Selection halogen, amino, cyano group, nitro, hydroxyl or the sulfydryl of the substituent independence；
And formula（I）Described in-R2Represent the optional position of phenyl ring where it, the para postion preferably on phenyl ring.
More specifically, the R1The independent alkyl selected from C3 ~ C20, C10 ~ C40 aryl, C10 ~ C40 aralkyl, Or C7 ~ C30 heteroaryl, the aryl of alkyl, C12 ~ C25, C12 ~ C25 aryl alkyl or C10 most preferably from C5 ~ C10 ~ C20 heteroaryl, specifically,
R 1Independent is selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro- ethyls of 2-, 2- cyano-propyls, isopropyl, tertiary fourth Base, pentyl, heptane base, dodecyl, formula（001）- formula（017）Structure；
Formula（001）,Formula（002）,Formula（003）,Formula（004）,Formula（005）,Formula（006）, Formula（007）,Formula（008）,Formula（009）,Formula（010）,Formula（011）,Formula（012）,Formula（013）,Formula （014）,Formula（015）,Formula（016）,Formula（017）；
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.And-Ra can be in any of the substituent Position, the preferably contraposition in substituent connecting key；And the number of the Ra in substituent is 0 ~ 5, more preferably 0,1 or 2；
Represent substituent and the connecting key of compound.
The R2Independent is selected from hydrogen, halogen, cyano group, C3 ~ C20 alkyl, C10 ~ C40 aryl, C10 ~ C40 aralkyl Base, C10 ~ C40 alkoxy aryl, C10 ~ C40 aryl alkane sulfydryl or C7 ~ C30 heteroaryl, most preferably hydrogen, halogen, cyanogen Base, C5 ~ C10 alkyl, C12 ~ C25 aryl, C12 ~ C25 aryl alkyl, C12 ~ C25 alkoxy aryl, C12 ~ C25 The heteroaryl of aryl alkane sulfydryl or C10 ~ C20, specifically,
R2Independent is selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro- ethyls of 2-, 2- cyano-propyls, isopropyl, tertiary fourth Base, pentyl, heptane base, dodecyl, formula（001）~ formula（021）Structure；
Formula（001）,Formula（002）,Formula（003）,Formula（004）,Formula（005）,Formula（006）, Formula（007）,Formula（008）,Formula（009）,
Formula（010）,Formula（011）,Formula（012）,Formula（013）,Formula（014）,Formula（015）,Formula（016）,Formula（017）,Formula（018）,Formula（019）,Formula（020）,Formula（021）；
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.And-Ra can be in any of the substituent Position, the preferably contraposition in substituent connecting key；And the number of the Ra in substituent is 0 ~ 5, more preferably 0,1 or 2；
Represent substituent and the connecting key of compound.
More specifically, it is described that there is formula（I）The compound of structure is Formulas I -1- Formulas I -12
Formulas I -1,Formulas I -2,
Formulas I -3,Formulas I -4,
Formulas I -5,Formulas I -6,
Formulas I -7,Formulas I -8,
Formulas I -9,Formulas I -10,
Formulas I -11,Formulas I -12.
Present invention also offers one kind to have formula（I）The preparation method of structural compounds, including：
There to be formula（II）The compound and formula of structure（III）The compound reaction of structure, obtains formula（IV）The change of structure Compound,Formula（II）,Formula（III）,Formula （IV）；
R1It is independent selected from hydrogen, halogen, cyano group, C1 ~ C30 alkyl, C6 ~ C50 aryl, C7 ~ C50 aryl alkyl, C7 ~ C50 alkoxy aryl, C7 ~ C50 aryl alkane sulfydryl or C5 ~ C50 heteroaryl；
X1And X2Independently selected from halogen, and it is not same halogen.
There to be formula（IV）The compound and formula of structure（V）The compound reaction of structure, obtains formula（I）The chemical combination of structure Thing；
Formula（V）,Formula（I）,
R2It is independent selected from hydrogen, halogen, cyano group, C1 ~ C30 alkyl, C6 ~ C50 aryl, C7 ~ C50 aryl alkyl, C7 ~ C50 alkoxy aryl, C7 ~ C50 aryl alkane sulfydryl or C5 ~ C50 heteroaryl；
Wherein, formula（II）Can be by formula（A）The compound and structural formula of structure（C）The compound of production B structure is reacted, Structural formula（B）Compound continues and benzophenone reaction production（II）The compound of structure；
Formula（A）,Formula（B）,Formula（C）,Formula（II）；
Wherein, formula（C）Middle X1And X2Independently selected from halogen, and it is not same halogen.
According to the present invention, the present invention will have formula（II）The compound and formula of structure（III）The compound reaction of structure, is obtained To formula（IV）The compound of structure, wherein, R1And R2The selection of group is as hereinbefore；The formula（II）The compound of structure with Formula（III）The mol ratio of the compound of structure is 1：（0.9~1.6）；The catalyst of the reaction is preferably tetra-triphenylphosphine palladium； The alkali of the reaction is sodium carbonate；The temperature of the reaction is preferably 130 ~ 180 DEG C, preferably 150 ~ 160 DEG C；The reaction Time is preferably 20 ~ 40 hours, more preferably 24 ~ 30 hours.
The present invention is to formula（II）The compound and formula of structure（III）The source of the compound of structure is not particularly limited, and is led to Preparation method well known in the art is crossed to be made.
According to the present invention, the present invention will have formula（IV）The compound and formula of structure（V）The compound reaction of structure, is obtained Formula（I）The compound of structure；Wherein, R1And R2The selection of group is as hereinbefore；The formula（IV）The compound and formula of structure （V）The mol ratio of the compound of structure is 1：（0.9~1.6）；Alkali used is sodium tert-butoxide in the reaction, and the reaction is urged Agent is acid chloride and tri-butyl phosphine；The temperature of the reaction is preferably 130 ~ 180 DEG C, preferably 150 ~ 160 DEG C；It is described anti- The time answered is preferably 20 ~ 40 hours, more preferably 24 ~ 30 hours.
According to the present invention, the present invention will have formula（A）The compound and formula of structure（C）The compound reaction of structure, is obtained Formula（B）The compound of structure, wherein, R1The selection of group is as hereinbefore；The formula（A）The compound and formula of structure（C）Knot The mol ratio of the compound of structure is 1：（0.9~1.6）；The catalyst of the reaction is preferably palladium；The alkali of the reaction is uncle Sodium butoxide；The temperature of the reaction is preferably 130 ~ 180 DEG C, preferably 150 ~ 160 DEG C；The time of the reaction is preferably 20 ~ 40 hours, more preferably 24 ~ 30 hours.
According to the present invention, the present invention will have formula（B）The compound of structure is reacted with benzophenone, obtains formula（II）Structure Compound, wherein, R1The selection of group is as hereinbefore；The formula（B）The compound of structure and the mol ratio of benzophenone For 1：（0.9~1.6）；The catalyst of the reaction is preferably n-BuLi；The alkali of the reaction is sodium tert-butoxide；The reaction Temperature be preferably -80 DEG C ~ -75 DEG C；More preferably -78 DEG C；The time of the reaction is preferably 0.5 ~ 4 hour, more preferably 1 ~ 3 hours.
Present invention also offers a kind of formula of the present invention（I）The compound of structure is preparing organic electroluminescence device In application；
Specifically, the organic electroluminescence device is preferably, including：
First electrode, second electrode and the organic matter layer being placed between two electrode, wherein, wrapped in the organic matter layer Contain formula（I）The compound of shown structure；Formula（I）The compound of shown structure can be single form or be mixed with other materials It is present in organic matter layer.
Wherein, the organic matter layer comprises at least hole injection layer, hole transmission layer, had both possessed hole injection but also with sky Technical ability layer is transmitted in cave, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both possesses electronics biography One or more in the defeated technical ability layer but also with electron injection.
The hole injection layer, the hole transmission layer, it is described both possessed hole injection but also with hole transport technical ability layer In at least one be conventional hole injecting material, hole transporting material or both possess hole injection but also with hole transport Technical ability material, it is also possible to be the material of electron-transporting material generation.
" organic matter layer " refers to the whole disposed between organic electronic device first electrode and second electrode in this patent The term of layer.
Specifically, work as formula（I）When the compound of structure is present in the luminescent layer in the organic layer, the formula（I）Structure Compound can be used as and light emitting host or be entrained in other fluorescent hosts；Such as：Luminescent layer can be red, yellow or Cyan luminescent layer.And by formula（I）Structure it is compound doped in cyan main body, the obtained effect of luminescent device can be provided Rate, brightness, resolution ratio and long-life.
Work as formula（I）When the compound of structure is present in electron transfer layer, the electron transfer layer also includes containing metal Compound.
When the organic layer includes luminescent layer and electron transfer layer, the formula（I）The compound of structure may reside in Wherein one layer or two layers.
It is of the present invention to include formula（I）Device prepared by the compound of structure can be used for organic luminescent device （OLED）, organic photovoltaic cell（OSC）, Electronic Paper（e-Paper）, Organophotoreceptor（OPC）Or OTFT （OTFT）.
Device of the present invention can by the methods of film vapor deposition, electron beam evaporation, physical vapour deposition (PVD) in substrate Upper evaporation metal and conductive oxide and their alloy form anode, can also use spin-coating（spin- coating）Or strip takes the lead to be deposited；Shaping can also be used（tape-casting）, scraping blade method（doctor-blading）, silk Wire mark brush（Screen-Printing）, ink jet printing or number of plies manufacture is reduced the methods of thermal imaging (Thermal-Imaging).
Compared with prior art, the present invention proposes a kind of organic compound, and it is by with high electron hole efficiency of transmission Acridine functional group imported with the spiro structure with structural rigidity and high thermal stability in the design of chemical constitution, with hole The excellent tri-arylamine group of transmission performance and excellent electron transport material 9, the combination of 9- dimethyl fluorenes, form a kind of heat endurance Can be high, the excellent compound of luminous efficiency, the introducing of different substituents, electron transition can be changed, adjust its luminous peak position Section, the red device being fabricated to the material of the present invention disclosure satisfy that the demand of industrialized production.
Embodiment：
It is clearly and completely described below in conjunction with the technical scheme of the embodiment of the present invention, it is clear that described implementation Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects Enclose.
Intermediate formula（B）The preparation of structural compounds
100ml two-neck bottles are taken to be respectively put into the bromo- 2- iodobenzenes 12.0mmol of 10.0mmol initiation materials, 1-, sodium tert-butoxide 25.0mmol, degassing is three times, it is ensured that and W-response be in nitrogen system, addition dry toluene solvent 30ml, and by reaction bulb On return duct reflux condensation mode, be eventually adding palladium 0.5mmol, heat temperature raising backflow, after reaction 24 hours, use TLC pieces It is determined that reaction terminates, room temperature is down to, is filtered, and is filtered and cleaned with dichloromethane, collects filtrate, rotary evaporation obtains slightly yellow liquid Body, column chromatography, use n-hexane/ethyl acetate=9:1 is eluent, carries out purifies and separates, can finally obtain product B, yield is about 70%。
Formula（B-2）~ formula（B-7）Synthetic method and formula（B-1）Synthetic method it is similar, its synthesize raw material and product 1 is shown in Table with yield；
The formula of table 1（B-2）~ formula（B-7）Shown product and its raw material and yield
Intermediate formula（II）The preparation of structural compounds
After taking 100ml two-neck bottles to insert 10.0mmol compounds A, degassing is three times, it is ensured that and W-response is in nitrogen system, Anhydrous THF solvents 20ml is added, reaction bulb is placed in -78 DEG C of cryogenic systems afterwards, after total system temperature reaches balance, Use needle aspirate n-BiLi 12.0mmol（1.6M is in n-hexane）Slowly it is added drop-wise in reaction bulb, maintains low-temp reaction 1 small Shi Hou, then benzophenone 10.0mmol is added in reaction bulb, maintains low-temp reaction after 1 hour, then by benzophenone 10.0mmol is added in reaction bulb, allows W-response slowly to be reacted to room temperature by -78 DEG C.After reacting two hours at room temperature, Reaction bulb is connected into upper return-flow system, and adds acetic acid 30ml, hydrochloric acid 3ml and begins to warm up backflow for cosolvent, is reacted 3 hours Afterwards, allow solution to return to room temperature, then extracted with dichloromethane, the organic liquor extracted respectively with saturated aqueous common salt with it is anhydrous Magnesium sulfate is dehydrated, and gray solid can be obtained by finally draining solvent, then can be obtained with dichloromethane and n-hexane progress reprecipitation Pure white product II, yield 50%.
Formula（II -2）~ formula（II -7）Synthetic method and formula（II -1）Synthetic method it is similar, its synthesize raw material with And product and yield are shown in Table 2；
The formula of table 2（II -2）~ formula（II -7）Shown product and its raw material and yield
Intermediate formula（IV）The preparation of structural compounds
Under nitrogen protection system, 10.0mmol intermediate IIs -1 and 12.0mmol is added to bromo-iodobenzene, adds sodium carbonate 25mmol and solvent 30ml, solvent are toluene and water, ratio 2:1, reaction system is deaerated, adds the triphenylphosphine of catalyst four Palladium 0.2mmol, the temperature of reaction system is risen into backflow, reacts 24 hours, uses petroleum ether：Dichloromethane=2:1 recrystallization, Obtain intermediate compound IV -1, yield 60%.
Formula（IV-2）~ formula（IV-7）Synthetic method and formula（IV-1）Synthetic method it is similar, its synthesize raw material and Product and yield are shown in Table 3；
The formula of table 3（IV-2）~ formula（IV-7）Shown product and its raw material and yield
Intermediate formula（V）The preparation of compound
By [1,1'- biphenyl] -4- amine 10.0mmol and 2- bromo- 9,9- dimethyl -9H- fluorenes 10.0mmol, 0.3mmol acetic acid Palladium, 0.3mmol tri-butyl phosphine, sodium tert-butoxide 25.0mmol, toluene 30ml, 7.5mmol target products are obtained, reaction terminates Ultra-pure water stirring is added afterwards, is filtered, and ethanol and ultrapure water wash, product V-1 is obtained after drying.
Formula（V-2）~ formula（V-7）Synthetic method and formula（V-1）Synthetic method it is similar, its synthesize raw material and product 4 are shown in Table with yield；
The formula of table 4（V-2）~ formula（V-7）Shown product and its raw material and yield
Target product formula（I）The preparation of structural compounds
Embodiment 1
By 10mmol intermediate compound IVs -1 and N-（[1,1'- biphenyl] -4- bases）- 9,9- dimethyl -9H-fluorenes -2- amine 15mmol, acid chloride 0.3mmol, tri-butyl phosphine 0.3mmol, sodium tert-butoxide 25mmol, toluene 30ml, reaction add after terminating Ultra-pure water stirs, and filters, and ethanol and ultrapure water wash, target product 5.6mmol target products, yield 56% is obtained after drying.By Test mass spectrum：844.37, elementary analysis：C:90.98 H:5.72 N:3.30.
The synthetic method of product shown in 2 ~ embodiment of embodiment 12 is similar with the synthetic method of embodiment 1, its original synthesized Material and product and yield are shown in Table 5, and table 5 is the product and its raw material and yield shown in 2 ~ embodiment of embodiment 12.
Product and its raw material and yield shown in the 2 ~ embodiment of embodiment 12 of table 5
With the preparation method of embodiment 1, replacing structure formula（1）Middle R1And R2Substituent can obtain different target products, Here just do not enumerate.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention Protect scope.
To obtained formula（I）Shown compound carries out performance test
The ito glass substrate that Fisher Co., Ltd's coating layer thickness is 1500 is placed in distilled water and cleaned 2 times, ultrasonic wave is washed Wash 30 minutes, wash 30 minutes, cleaned repeatedly with distilled water 2 times in order by isopropanol, acetone, methanol, ultrasonic washing 10 Minute, dry, be transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, is sent in evaporator.Having been prepared for It is 60mm, material of main part layer a-NPD that hole injection layer 2-TNATA vacuum evaporations thickness is deposited successively on good ito transparent electrode Or the material vacuum evaporation thickness of embodiment 1- embodiments 12 described in table 5 is 20nm, dopant material layer is according to 90:10 doping CBP and Ir（ppy）3Vacuum evaporation thickness is 30nm, and hole blocking layer and electron transfer layer BAlq vacuum evaporations thickness are 10nm, AlQ3 thickness is 40nm, negative electrode LiF thickness is 0.2nm, and Al thickness is 150nm.
Evaporation is finished to obtain luminescent device, and the performance characteristics of luminescence of the device to obtaining is tested, and measurement uses KEITHLEY The type source measuring unit of Keithley 2400, CS-2000 spectroradio luminance meters, to evaluate driving voltage, luminosity, light effect Rate.6 are the results are shown in Table, table 6 is the luminous spy of 1-12 compounds prepared by the embodiment of the present invention and luminescent device prepared by a-NPD Property test result.
The luminescent device that table 6 is compound prepared by the embodiment of the present invention and prepared by a-NPD
Characteristics of luminescence test result
Increased significantly from the luminous efficiency of the knot of table 6 compound provided by the invention and life-span relative to a-NPD.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.

Claims (5)

  1. A kind of 1. electroluminescent organic material, it is characterised in that the general structure of the luminous organic material such as formula（1）It is shown：
    Formula（1）；
    Wherein, R1For、、、、、、； R2For、、、、、、、 ,For connection site.
  2. 2. compound according to claim 1, it is characterised in that described that there is formula（I）The compound of structure be Formulas I -1 ~ I-12：
    Formulas I -1,Formulas I -2,
    Formulas I -3,Formulas I -4,
    Formulas I -5,Formulas I -6,
    Formulas I -7,Formulas I -8,
    Formulas I -9,Formulas I -10,
    Formulas I -11,Formulas I -12.
  3. 3. one kind has formula（I）The preparation method of structural compounds, including：There to be formula（IV）The compound and formula of structure（V） The compound reaction of structure, obtains formula（I）The compound of structure；
    Formula（V）,Formula（IV）,
    Formula（I）；
    Wherein, R1For、、、、、、； R2For、、、、、、、 ,For connection site； X1Independently selected from halogen, and it is not same halogen Element.
  4. 4. one kind according to claim 3 has formula（I）The preparation method of structural compounds, it is characterised in that one kind tool There is formula（IV）The preparation method of structural compounds, including：
    There to be formula（II）The compound and formula of structure（III）The compound reaction of structure, obtains formula（IV）The compound of structure,Formula（II）,Formula（III）,Formula（IV）；
    Wherein, R1For、、、、、、；For connection site；X1And X2Independently selected from halogen, and it is not same halogen.
  5. A kind of 5. formula shown in claim 1 ~ 2 any one（I）Preparation method described in compound and claim 3 ~ 4 obtains The formula arrived（I）Application of the compound in organic electroluminescence device is prepared.
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CN109180581A (en) * 2018-10-11 2019-01-11 吉林奥来德光电材料股份有限公司 A kind of organic luminescent compounds and preparation method and the organic luminescent device containing the compound
WO2020073605A1 (en) * 2018-10-11 2020-04-16 上海升翕光电科技有限公司 Organic luminescent compound, preparation method therefor and organic electroluminescent device containing same
CN109336812A (en) * 2018-10-11 2019-02-15 吉林奥来德光电材料股份有限公司 Organic luminescent compounds and preparation method thereof and organic electroluminescence device containing the compound
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