CN106349251B - One kind including 4,5- diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device - Google Patents
One kind including 4,5- diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device Download PDFInfo
- Publication number
- CN106349251B CN106349251B CN201610709715.3A CN201610709715A CN106349251B CN 106349251 B CN106349251 B CN 106349251B CN 201610709715 A CN201610709715 A CN 201610709715A CN 106349251 B CN106349251 B CN 106349251B
- Authority
- CN
- China
- Prior art keywords
- layer
- substitution
- formula
- substituted
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C[C@@](C=*=C(/C=C1)Br)C(C2=NC(Br)=CCC22)=C1OC2(C1=C2CC=CC=C1)C(/C=C/C=*=CC1)=C1S2(=O)=O Chemical compound C[C@@](C=*=C(/C=C1)Br)C(C2=NC(Br)=CCC22)=C1OC2(C1=C2CC=CC=C1)C(/C=C/C=*=CC1)=C1S2(=O)=O 0.000 description 3
- CSFXWKWDDBWPGY-UHFFFAOYSA-N C(C1)C=CC2=C1Nc1ccccc1S2 Chemical compound C(C1)C=CC2=C1Nc1ccccc1S2 CSFXWKWDDBWPGY-UHFFFAOYSA-N 0.000 description 1
- FROGWEJVFCZOLJ-UHFFFAOYSA-N C=[Br]c(cc1C23c(cccc4)c4Sc4c2cccc4)cnc1-c1c3cccn1 Chemical compound C=[Br]c(cc1C23c(cccc4)c4Sc4c2cccc4)cnc1-c1c3cccn1 FROGWEJVFCZOLJ-UHFFFAOYSA-N 0.000 description 1
- YDNISPZFLPYSSJ-UHFFFAOYSA-N CC(C)(C1C2)c3ccccc3C1=Cc1c2[nH]c2ccccc12 Chemical compound CC(C)(C1C2)c3ccccc3C1=Cc1c2[nH]c2ccccc12 YDNISPZFLPYSSJ-UHFFFAOYSA-N 0.000 description 1
- ROERIJHPIVWLBX-UHFFFAOYSA-N CC1(C)c2ccccc2N(c(cc2C34c(cccc5)c5S(C)c5c3cccc5)cnc2-c(nc2)c4cc2N(c2c(C3(C)C)cccc2)c2c3cccc2)c2c1cccc2 Chemical compound CC1(C)c2ccccc2N(c(cc2C34c(cccc5)c5S(C)c5c3cccc5)cnc2-c(nc2)c4cc2N(c2c(C3(C)C)cccc2)c2c3cccc2)c2c1cccc2 ROERIJHPIVWLBX-UHFFFAOYSA-N 0.000 description 1
- JSEQNGYLWKBMJI-UHFFFAOYSA-N CC1(C)c2ccccc2Nc2ccccc12 Chemical compound CC1(C)c2ccccc2Nc2ccccc12 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/20—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to field of organic electroluminescent materials, including 4,5 diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device more particularly to one kind, can be used for Organic Light Emitting Diode, and with bipolar transmission property well, it can be used as material of main part use.Structural formula is as follows：Wherein, Ar1、Ar2It is independent to be selected from hydrogen atom, C3~C30Substitution or non-substituted carbazole group, C3~C30Substitution or non-substituted arylamine group, C3~C30Substitution or non-substituted phenthazine group, C3~C30Substitution or non-substituted phenoxazine group, C3~C30Substitution or non-substituted azophenlyene group, C3~C30Substitution or non-substituted acridine group, Ar1、Ar2It is asynchronously hydrogen.The invention further relates to a kind of including at least one layer of bipolarity compound as the device of material of main part and the method for manufacturing the device.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, and in particular to one kind includes 4,5- diaza spiro formula thioxanthene knots
Structure electroluminescent organic material and its application and device.
Background technology
Phosphor material can take full advantage of account for 75% ratio three that electron-hole recombinations generate in electroluminescent device
Line state exciton, intersystem crossing, which occurs, for singlet exciton can make the exciton utilization rate of phosphorescent devices to the transfer of the triplet state of more low-lying level
Even it can reach 100%.Phosphor material is entrained in usually as guest materials in material of main part, and effective material of main part should have
There is ideal band gap to make energy be efficiently transferred to object, good carrier transport property carries to be realized in emission layer
The balance recombination of stream, the level-density parameter with adjacent layer is to realize that effective charge injects, and enough heat and morphology are stablized
Property to extend device lifetime, therefore the exploitation of material of main part shine for efficient electroluminescent phosphorescence it is of crucial importance.
Traditional material of main part usually only has single carrier transport property, this unbalanced carrier transport property
Have shown that the cut-in voltage to OLED and the unfavorable property in service life.Develop new material of main part requirement must have it is bipolar
Carrier (hole and electronics) injects and transport property, adds up between luminescent layer and charge transport layer to avoid carrier, draws
Interface Exciplex emission is played, causes the major parameters such as the external quantum efficiency, power efficiency, current efficiency of device relatively low,
Open phenomena such as bright voltage is higher, and spectrum is unstable.Therefore, in recent years can equilbrium carrier transmission bipolar material of main part cause
Sizable concern.
Invention content
Technical problem to be solved by the invention is to provide a kind of electroluminescent organic material and its application, the present invention relates to
A kind of electroluminescent organic material including 4,5- diaza spiro formula thioxanthene structures.This electroluminescent organic material has fine
Thermodynamic stability, good film forming and carrier transport ability, shown in structure such as formula general formula (1)：
Wherein, Ar1、Ar2It is independently selected from hydrogen atom, C3~C30Substitution or non-substituted carbazole group, C3~
C30Substitution or non-substituted arylamine group, C3~C30Substitution or non-substituted phenthazine group, C3~C30Substitution is non-
Substituted phenoxazine group, C3~C30Substitution or non-substituted acridine group, Ar1、Ar2It is asynchronously hydrogen.
Inventor is found surprisingly that under study for action, bipolarity main body electroluminescent organic material of the present invention have with
Lower advantage：
1. bipolarity main body electroluminescent organic material of the present invention has the injection of higher carrier and transmittability.
2. bipolarity main body electroluminescent organic material of the present invention has higher glass transition temperature and thermal decomposition
The advantages that temperature, the stability of compound is high.
3. bipolarity main body electroluminescent organic material of the present invention has higher singlet and triplet, into
One step can be used as the use of blue and green light material of main part.Using the organic compound of the present invention as material of main part, the device of preparation
External quantum efficiency, power efficiency and current efficiency can effectively be promoted.
Further, the Ar1、Ar2It is independently selected from lower structure：
The beneficial effects of adopting the above-mentioned further technical scheme are as follows：Inventor is found surprisingly that under study for action, Ar1、Ar2Solely
Vertical is selected from above-mentioned group, is conducive to the thermal stability and carrier transport efficiency that promote material.
Further, the structural formula of compound is preferably selected from any one in the structural formula in C1-C52：
Compound C01-C52 is the representative structure or preferred structure for meeting spirit of that invention and principle, it should be understood that row
Go out above compound structure, is intended merely to preferably explain the present invention, is not limitation of the present invention.
The beneficial effects of adopting the above-mentioned further technical scheme are as follows：Above-mentioned compound C01-C52, by experimental verification,
Have many advantages, such as thermodynamic stability, good carrier transport property, good film forming well.
The present invention also provides application of the above-mentioned bipolarity main body electroluminescent organic material in field of organic electroluminescence.
The bipolarity main body electroluminescent organic material can be used as material of main part, especially as Blue-light emitting host material or green light main body
Material.
Such as：It is used for field of organic electroluminescence using above-mentioned material as green light material of main part, in particular for Organic Electricity
The luminescent layer of electroluminescence device.During specific application, the implementation process with as a result, being intended merely to preferably explain
The present invention is not limitation of the present invention.
The present invention provides a kind of organic electroluminescence device, including：
Anode, cathode and the organic luminescence function layer between the anode and the cathode, wherein described organic
Light emitting functional layer includes above-mentioned bipolarity main body electroluminescent organic material.
If organic light emitting functional layer is equipped with multiple, at least one organic luminescence function layer contains above-mentioned bipolarity master
Body electroluminescent organic material.
Using having the beneficial effect that for above-mentioned technical proposal：Due to bipolarity main body electroluminescent organic material of the present invention
Dipole characteristic with good transporting holes and electronics, it is bright with opening using the organic electroluminescence device of this material preparation
The advantages that voltage is low, luminous efficiency is high；Bipolarity main body electroluminescent organic material of the present invention has higher vitrifying
The stability of transition temperature and heat decomposition temperature, compound is high, is conducive to the service life for significantly improving device；It is of the present invention bipolar
Property main body electroluminescent organic material have higher singlet and triplet, it is preferable that can be used as green light material of main part
It uses.Using bipolarity main body electroluminescent organic material of the present invention as material of main part, the device of preparation can be effective
Promotion external quantum efficiency, power efficiency and current efficiency.
Further, the organic luminescence function layer include hole injection layer, hole transmission layer, luminescent layer, electron transfer layer,
Any one in electron injecting layer, hole blocking layer, electronic barrier layer or arbitrary several combination.
Further, the luminescent layer includes material of main part and guest emitting material, wherein the material of main part includes described
Bipolarity main body electroluminescent organic material.
By taking green light OLED device as an example, the ITO Conducting Glass (anode) being sequentially overlapped, hole injection layer are generally comprised
(HATCN), hole transmission layer (TAPC), luminescent layer (electroluminescent organic material of the present invention), electron transfer layer
(TmPyPB), electron injecting layer (LiF) and cathode layer (Al).All functional layers are all made of vacuum evaporation process and are made.Such device
The molecular structural formula of some used organic compounds is as follows in part.
In the present invention, the functional layer of device is not limited to use above-mentioned material, these materials that can be replaced with other materials,
Can be replaced with NPB to device performance to be further improved, such as hole transmission layer, electron transfer layer can use TpPyPB,
The molecular structural formula of the replacements such as TPBi, these materials is as follows：
Description of the drawings
Fig. 1 is the structural schematic diagram of organic electroluminescence device prepared by the present invention, by lower layer to upper layer, be followed successively by 101,
ITO Conducting Glass, 102, hole injection layer, 103, hole transmission layer, 104, luminescent layer, 105, electron transfer layer, 106,
Electron injecting layer, 107, cathode layer, wherein luminescent layer is related to electroluminescent organic material of the present invention.
Specific implementation mode
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1：The preparation of intermediate M1
Under the conditions of nitrogen protection, diphenyl sulphone (DPS) (10.9g, 0.05mol), tetrahydrofuran are added into 500mL three-necked flasks
(109mL).Bath temperature is set as -85 DEG C, stirring cooling.Interior temperature drop starts the hexane solution that n-BuLi is added dropwise to -80 DEG C
(24mL, 2.5M), control drop speed, keeps interior temperature to be less than -80 DEG C.It is added dropwise, insulation reaction 3h, moves under the conditions of 25 DEG C of room temperature
Stirring heating 2h.The tetrahydrofuran (100mL) of bromo- [2,2'- the bipyridyl] -3- methyl formates (14.6g, 0.05mol) of 5- is added dropwise
Solution.It is added dropwise, 10h is stirred under the conditions of 25 DEG C of room temperature.Reaction is quenched in 100mL saturated aqueous ammonium chlorides, and hydrolysis generates phase
The alcohols intermediate answered.Liquid separation retains upper organic phase, and anhydrous sodium sulfate dries organic phase, directly crosses column, crosses column liquid precipitation
Agent obtains 21.5g off-white powder shape solids.
It is added above-mentioned gained alcohols intermediate into 500mL there-necked flasks, 200mL toluene, p-methyl benzenesulfonic acid (0.95g,
0.005mol), under the conditions of nitrogen protection, 110 DEG C of interior temperature is stirred at reflux 3h, and TLC monitors reaction process.Reaction finishes, and will react
Liquid pours into 300mL water phases, liquid separation, 200mL ethyl acetate aqueous phase extracteds, liquid separation, merges organic phase.Anhydrous sodium sulfate is dried,
It filters, desolventizing obtains light yellow powder solid.The isolated 12.4g off-white powders shape intermediate M1 of silica gel column chromatography is received
Rate：54%.
Mass spectrum MS (m/e), molecular formula C23H13BrN2O2S, theoretical value 459.9, test value 459.0.
Elemental analysis (C23H13BrN2O2S), theoretical value C：59.88%, H：2.84%, Br:17.32 O：6.94%, N：
6.07%, S：6.95%；Measured value C：59.77%, H：2.74%, Br:17.35 O：7.01%, N：6.07%, S：7.06%.
Embodiment 2：The preparation of intermediate M2
Using the method similar with embodiment 1,6- bromo- [2,2'- the bipyridyl] -3- methyl formate generations using equivalent
For bromo- [2,2'- the bipyridyl] -3- methyl formates of 5-, other conditions are constant, obtain intermediate M2, off-white powder 5.3g, yield
23%.
Mass spectrum MS (m/e), molecular formula C23H13BrN2O2S, theoretical value 459.9, test value 459.6.
Elemental analysis (C23H13BrN2O2S), theoretical value C：59.88%, H：2.84%, Br:17.32 O：6.94%, N：
6.07%, S：6.95%；Measured value C：59.87%, H：2.79%, Br:17.40 O：6.99%, N：6.10%, S：6.85%.
Embodiment 3：The preparation of intermediate M3
Using the method similar with embodiment 1, bromo- [2,2'- the bipyridyl] -3- formic acid of 5,5'- bis- using equivalent
Methyl esters replaces bromo- [2,2'- the bipyridyl] -3- methyl formates of 5-, and other conditions are constant, obtain intermediate M3, off-white powder
11.3g, yield 42%.
Mass spectrum MS (m/e), molecular formula C23H12Br2N2O2S, theoretical value 537.9, test value 538.1.
Elemental analysis (C23H12Br2N2O2S), theoretical value C：51.14%, H：2.24%, Br:29.58 O：5.92%, N：
5.19%, S：5.94%；Measured value C：51.22%, H：2.25%, Br:29.47 O：5.95%, N：5.20%, S：5.91%.
Embodiment 4：The preparation of intermediate M4
Using the method similar with embodiment 1, bromo- [2,2'- the bipyridyl] -3- formic acid of 6,6'- bis- using equivalent
Methyl esters replaces bromo- [2,2'- the bipyridyl] -3- methyl formates of 5-, and other conditions are constant, obtain intermediate M4, off-white powder
5.1g, yield 19%.
Mass spectrum MS (m/e), molecular formula C23H12Br2N2O2S, theoretical value 537.9, test value 537.3.
Elemental analysis (C23H12Br2N2O2S), theoretical value C：51.14%, H：2.24%, Br:29.58 O：5.92%, N：
5.19%, S：5.94%；Measured value C：51.16%, H：2.22%, Br:29.57 O：5.95%, N：5.15%, S：5.95%.
Embodiment 5：The preparation of compound C1
Under nitrogen environment, successively into 250ml there-necked flasks be added M1 (4.6g, 0.01mol), carbazole (2g, 0.012mol),
N, N- dimethyl propylene alkenyl urea (DMPU) (100mL), cuprous iodide (190mg, 0.001mol), 18-C-6 (528mg,
0.002mol)、K2CO3(4.2g, 0.03mol).Bath temperature is set as 155 DEG C, and stirred under nitrogen atmosphere reacts 16.0h, TLC monitorings
Raw material is cooled to room temperature after the reaction was complete.Dichloroethanes extracts, liquid separation, merges organic phase, and anhydrous sodium sulfate drying filters, filter
Liquid desolventizing.Column chromatography purifies, and purification ＆ isolation obtains 3.6g white powdery solids, yield 66%.
Embodiment 6：The preparation of compound C2
Using the method similar with embodiment 5, M1 is replaced using the M2 of equimolar equivalent, other conditions are constant, obtain
C2, white solid 2.5g, yield 45%.
Embodiment 7：The preparation of compound C3
Using the method similar with embodiment 5, carbazole is replaced using 3, the 6- di-t-butyl carbazoles of equimolar equivalent,
His condition is constant, obtains C3, white solid 2.2g, yield 33%.
Embodiment 8：The preparation of compound C5
Under nitrogen environment, successively into 250ml there-necked flasks be added M1 (4.6g, 0.01mol), diphenylamines (2g,
0.012mol), after 15min is stirred at room temperature, palladium is added in ortho-xylene (100mL), sodium tert-butoxide (2.9g, 0.03mol)
(22.5mg, 0.1mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls (S-phos) (84mg, 0.2mmol).Bath temperature is set
It is set to 150 DEG C, stirred under nitrogen atmosphere reacts 12.0h, and TLC monitorings raw material is cooled to room temperature after the reaction was complete.Wash organic phase
To neutrality, liquid separation, anhydrous sodium sulfate dries organic phase, filters, filtrate desolventizing.Column chromatography purifies, and purification ＆ isolation obtains 4.1g
White powdery solids, yield 75%.
Embodiment 9：The preparation of compound C6
Using the method similar with embodiment 8, hexichol is replaced using 4, the 4`- di-t-butyl diphenylamines of equimolar equivalent
Amine, other conditions are constant, obtain C6, white solid 5.4g, yield 82%.
Embodiment 10：The preparation of compound C7
Using the method similar with embodiment 8, M1 is replaced using the M2 of equimolar equivalent, other conditions are constant, obtain
C7, white solid 2.4g, yield 44%.
Embodiment 11：The preparation of compound C10
Using the method similar with embodiment 5, replaced using 7H- benzofurans [2,3-b] carbazole of equimolar equivalent
Carbazole, other conditions are constant, obtain C10, white solid 3.8g, yield 60%.
Embodiment 12：The preparation of compound C12
Using the method similar with embodiment 5, carbazole is replaced using the intermediate M5 of equimolar equivalent, other conditions are not
Become, obtains C12, off-white powder 3.7g, yield 56%.
Embodiment 13：The preparation of compound C13
Using the method similar with embodiment 5, carbazole is replaced using the M6 of equimolar equivalent, other conditions are constant, obtain
To C13, white solid 4.6g, yield 65%.
Embodiment 14：The preparation of compound C15
Using the method similar with embodiment 5, M1, the M5 of equimolar equivalent is replaced to replace using the M2 of equimolar equivalent
Carbazole, other conditions are constant, obtain C15, white solid 3.8g, yield 57%.
Embodiment 15：The preparation of compound C19
Using the method similar with embodiment 8, diphenylamines is replaced using equimolar equivalent phenoxazines, other conditions are not
Become, obtains C19, white solid 1.7g, yield 30%.
Embodiment 16：The preparation of compound C20
Using the method similar with embodiment 8, diphenylamines is replaced using the phenthazine of equimolar equivalent, other conditions are not
Become, obtains C20, white solid 1.8g, yield 31%.
Embodiment 17：The preparation of compound C21
Using the method similar with embodiment 8, diphenylamines is replaced using 9, the 9- dimethyl acridiniums of equimolar equivalent,
His condition is constant, obtains C21, white solid 2.0g, yield 34%.
Embodiment 18：The preparation of compound C22
Using the method similar with embodiment 8, two are replaced using 5, the 10- dihydro -5- phenyl azophenlyene of equimolar equivalent
Aniline, other conditions are constant, obtain C22, white-yellowish solid 2.5g, yield 39%.
Embodiment 19：The preparation of compound C25
Using the method similar with embodiment 8, diphenylamines, other conditions are replaced using the intermediate M7 of equimolar equivalent
It is constant, obtain C25, white-yellowish solid 3.6g, yield 53%.
Embodiment 20：The preparation of compound C27
Using the method similar with embodiment 8, diphenylamines, other conditions are replaced using the intermediate M8 of equimolar equivalent
It is constant, obtain C27, white solid 2.2g, yield 31%.
Embodiment 21：The preparation of compound C31
Using the method similar with embodiment 8, diphenylamines, other conditions are replaced using the bigeminy aniline of equimolar equivalent
It is constant, obtain C27, white solid 3.5g, yield 50%.
Embodiment 22：The preparation of compound C33
Using the method similar with embodiment 8, diphenylamines, other conditions are replaced using the intermediate M9 of equimolar equivalent
It is constant, obtain C33, white solid 4.9g, yield 66%.
Embodiment 23：The preparation of compound C35
Using the method similar with embodiment 8, diphenylamines is replaced using the intermediate M10 of equimolar equivalent, other
Part is constant, obtains C35, white solid 5.0g, yield 73%.
Embodiment 24：The preparation of compound C38
Under nitrogen environment, successively into 250ml there-necked flasks be added M3 (5.4g, 0.01mol), phenoxazines (4g,
0.022mol), after 15min is stirred at room temperature, palladium is added in ortho-xylene (100mL), sodium tert-butoxide (2.9g, 0.03mol)
(22.5mg, 0.1mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls (S-phos) (84mg, 0.2mmol).Bath temperature is set
It is set to 150 DEG C, stirred under nitrogen atmosphere reacts 12.0h, and TLC monitorings raw material is cooled to room temperature after the reaction was complete.Wash organic phase
To neutrality, liquid separation, anhydrous sodium sulfate dries organic phase, filters, filtrate desolventizing.Column chromatography purifies, and purification ＆ isolation obtains 4.3g
White powdery solids, yield 58%.
Embodiment 25：The preparation of compound C39
Under nitrogen environment, successively into 250ml there-necked flasks be added M3 (5.4g, 0.01mol), carbazole (3.7g,
0.022mol), N, N- dimethyl propylene alkenyl urea (DMPU) (100mL), cuprous iodide (190mg, 0.001mol), 18-C-6
(528mg, 0.002mol), K2CO3(4.2g, 0.03mol).Bath temperature is set as 155 DEG C, and stirred under nitrogen atmosphere reacts 16.0h,
TLC monitorings raw material is cooled to room temperature after the reaction was complete.Dichloroethanes extracts, liquid separation, merges organic phase, and anhydrous sodium sulfate is dried,
It filters, filtrate desolventizing.Column chromatography purifies, and purification ＆ isolation obtains 5.2g white powdery solids, yield 73%.
Embodiment 26：The preparation of compound C45
Using with implement 24 similar methods, using equimolar equivalent 9,9- dimethyl acridiniums replace phenoxazine,
His condition is constant, obtains C45, white solid 5.0g, yield 63%.
Embodiment 27：The preparation of compound C47
Under nitrogen environment, M3 (5.4g, 0.01mol), duplex pinacol borate is added into 250ml there-necked flasks successively
After 15min is stirred at room temperature, four (triphenyls are added in (12.7g, 0.05mol), toluene (100mL), potassium carbonate (7g, 0.05mol)
Phosphine) palladium (116mg, 0.1mmol).Bath temperature is set as 100 DEG C, and stirred under nitrogen atmosphere reacts 12.0h, and TLC monitors raw material reaction
It is cooled to room temperature after completely.Column chromatography purifies, and purification ＆ isolation obtains 4g intermediates M11.
Under nitrogen environment, above-mentioned intermediate M11 (4.0g, 0.0063mol), 9- (4- is added into 250ml there-necked flasks successively
Bromophenyl) carbazole (4.5g, 0.014mol), toluene (150mL), potassium carbonate (2.6g, 0.019mol), after 15min is stirred at room temperature,
Be added palladium (67mg, 0.3mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls (S-phos) (252mg,
0.6mmol).Bath temperature is set as 110 DEG C, and stirred under nitrogen atmosphere reacts 10.0h, and TLC monitorings raw material is cooled to after the reaction was complete
Room temperature.Column chromatography purifies, and purification ＆ isolation obtains C47, white solid 6.7g, total recovery 77%.
Embodiment 28：The preparation of compound C51
Using the method similar with embodiment 27,9- (4- are replaced using 10- (4- bromophenyls) -9,9- dimethyl acridiniums
Bromophenyl) carbazole, molar ratio：10- (4- bromophenyls) -9,9- dimethyl acridiniums/M11=2.2/1, other conditions are constant, obtain
C51, white solid 6.5g, yield 68%.
Compound mass spectrum and elemental analysis：
Here is the Application Example of the compounds of this invention：
Embodiment 29：Prepare one-device of device eight
Preparation method：
A) ITO (tin indium oxide) glass is cleaned：Respectively each 30 points of ito glass is cleaned with deionized water, acetone, EtOH Sonicate
Then clock is handled 5 minutes in plasma cleaner；
B) the vacuum evaporation hole injection layer HAT-CN on anode ito glass, thickness 10nm；
C) the vacuum evaporation hole transmission layer TAPC on hole injection layer, thickness 40nm；
D) on hole transmission layer, vacuum evaporation luminescent layer bipolarity host compound:15%wt Ir (ppy)3, thick
Degree is 30nm；
E) on luminescent layer, TmPyPB, thickness 30nm of the vacuum mixing vapor deposition as electron transfer layer；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness 1nm；
G) on electron injecting layer, vacuum evaporation cathode Al, thickness 100nm.
The structure of device is ITO/HAT-CN (10nm)/TAPC (40nm)/bipolarity host compound:15%wt Ir
(ppy)3(30nm)/TmPyPB (30nm)/LiF (1nm)/Al (100nm), during vacuum evaporation, pressure<4.0×10-4Pa,
The test result of obtained device is shown in Table 1.
Comparative example 1：Organic electroluminescence device is made according to method identical with embodiment 29, difference lies in using 4,
(9H- the carbazoles) -1,1'- biphenyl of 4'- bis- (CBP) replaces bipolarity chemical combination prepared in embodiment as the main body of luminescent layer
Object.The test result of obtained device is shown in Table 1.
1 device photoelectric tables of data of table
In order to compare, present invention manufacture uses the parametric device of conventional body material C BP.With conventional body material C BP ratios
Compared with the organic electroluminescence device prepared based on material of main part of the present invention is shown in terms of efficiency, driving voltage and stability
Outstanding characteristic.Particularly, the higher characteristics of luminescence is shown in terms of efficiency, and material of main part of the present invention has significant pair
Pole characteristic.
The foregoing is merely preferred embodiments of the present invention, are not limitation of the present invention.The present invention is intended to provide one
Kind includes the spiral shell formula thioxanthene electroluminescent organic material of 4,5- diazas, the electroluminescent hair made with material provided by the present invention
Optical device, device performance have the space further promoted, such as use other materials to replace TAPC as hole transmission layer, use it
His material replaces TmPyPB as electron transfer layer, and luminescent layer etc. is made using the mode of other doping, and similar improve all should
It is understood to, belongs to the protection category of the present invention.
Claims (7)
1. one kind including the electroluminescent organic material of 4,5- diaza spiro formula thioxanthenes, which is characterized in that have general formula (1) institute
The structure shown,
Wherein, Ar1、Ar2It is independently selected from hydrogen atom, C3~C30Substitution or non-substituted carbazole group, C3~C30Substitution
Or non-substituted arylamine group, C3~C30Substitution or non-substituted phenthazine group, C3~C30Substitution is non-substituted
Phenoxazine group, C3~C30Substitution or non-substituted azophenlyene group, C3~C30Substitution or non-substituted acridine group, Ar1、
Ar2It is asynchronously hydrogen.
2. according to claim 1 includes the electroluminescent organic material of 4,5- diaza spiro formula thioxanthenes, feature exists
In the Ar1、Ar2It is independently selected from lower structure：
3. according to claim 1 includes the electroluminescent organic material of 4,5- diaza spiro formula thioxanthenes, feature exists
In any one of structural formula of compound in C1-C52：
4. a kind of organic electroluminescence material according to any one of claims 1 to 3 including 4,5- diaza spiro formula thioxanthenes
The application of material, it is characterised in that：As material of main part or charge transport materials.
5. a kind of organic electroluminescence device, which is characterized in that including:Anode, cathode and be located at the anode and described the moon
Organic luminescence function layer between pole, wherein the organic luminescence function layer includes described in any one of claims 1 to 3
The electroluminescent organic material for including 4,5- diaza spiro formula thioxanthenes.
6. organic electroluminescence device according to claim 5, it is characterised in that：The organic luminescence function layer includes sky
Appointing in cave implanted layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, hole blocking layer or electronic barrier layer
It anticipates one or more layers combination.
7. organic electroluminescence device according to claim 6, it is characterised in that：The hole transmission layer, luminescent layer
Or at least one of electron transfer layer include claims 1 to 3 any one described in include 4,5- diaza spiro formula sulphur
The electroluminescent organic material of miscellaneous anthracene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610709715.3A CN106349251B (en) | 2016-08-23 | 2016-08-23 | One kind including 4,5- diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610709715.3A CN106349251B (en) | 2016-08-23 | 2016-08-23 | One kind including 4,5- diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106349251A CN106349251A (en) | 2017-01-25 |
| CN106349251B true CN106349251B (en) | 2018-07-24 |
Family
ID=57844478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610709715.3A Active CN106349251B (en) | 2016-08-23 | 2016-08-23 | One kind including 4,5- diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106349251B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3733649A1 (en) * | 2019-04-29 | 2020-11-04 | Novaled GmbH | Hetero-fluorene derivatives and their use in electronic devices |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956962A (en) * | 2017-12-14 | 2019-07-02 | 江苏三月光电科技有限公司 | It is a kind of fluorene structured for the compound of parent nucleus and its application on organic electroluminescence device with azaspiro |
| CN110734448B (en) * | 2018-07-19 | 2021-09-24 | 北京绿人科技有限责任公司 | Organic compound, application thereof and organic electroluminescent device |
| CN110872290B (en) * | 2018-08-31 | 2022-05-13 | 北京绿人科技有限责任公司 | Organic electroluminescent compound, application thereof and organic electroluminescent device |
| CN111518126B (en) * | 2019-02-01 | 2023-08-22 | 北京绿人科技有限责任公司 | Nitrogen-containing organic compound, application thereof and organic electroluminescent device |
| CN111518109B (en) * | 2019-02-01 | 2021-10-01 | 北京绿人科技有限责任公司 | Organic compound, application thereof and organic electroluminescent device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006080638A1 (en) * | 2004-09-24 | 2006-08-03 | Lg Chem. Ltd. | New compound and organic light emitting device using the same (7) |
| KR102088637B1 (en) * | 2011-07-29 | 2020-03-13 | 메르크 파텐트 게엠베하 | Compounds for electronic devices |
| KR20130140303A (en) * | 2012-06-14 | 2013-12-24 | (주) 에프엔지리서치 | Novel compounds for organic electroluminescent device |
| KR101716069B1 (en) * | 2012-11-12 | 2017-03-13 | 메르크 파텐트 게엠베하 | Materials for electronic devices |
| KR102249277B1 (en) * | 2013-05-15 | 2021-05-07 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
| CN104193736B (en) * | 2014-08-22 | 2017-04-05 | 华南理工大学 | A kind of organic small molecule material based on spiral shell formula thioxanthene and using the material as the organic electro-optic device of luminescent layer |
-
2016
- 2016-08-23 CN CN201610709715.3A patent/CN106349251B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3733649A1 (en) * | 2019-04-29 | 2020-11-04 | Novaled GmbH | Hetero-fluorene derivatives and their use in electronic devices |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106349251A (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106349251B (en) | One kind including 4,5- diaza spiro formula thioxanthene structure electroluminescent organic materials and its application and device | |
| CN105884830B (en) | A kind of bipolarity OLED phosphorescent light body materials and the luminescent device comprising the material | |
| CN106905220B (en) | A kind of spirofluorene derivative and organic electroluminescence device | |
| TW201726644A (en) | Spiro structure having spiro structure, organic light emitting device comprising the same, display device and lighting device | |
| CN105440004B (en) | A kind of electroluminescent organic material and its application | |
| KR20110002155A (en) | New compounds and organic electronic device using the same | |
| CN108440524A (en) | A kind of Sanya benzene derivative and its organic electroluminescence device | |
| CN103509016B (en) | Bipyridine fluorene derivatives, preparation method and application thereof, and electroluminescent device | |
| WO2018157478A1 (en) | Fluoreno carbazole derivative and phosphorescent organic electroluminescent device | |
| CN112552275B (en) | Spiro compound and application thereof | |
| CN108276336A (en) | Organic photoelectric functional material, light-emitting device, and preparation method and application thereof | |
| CN108358919A (en) | A kind of phenanthrene derivative and its organic electroluminescence device | |
| CN109651423A (en) | A kind of dibenzo-heterocyclic compound and its preparation method and application | |
| CN105924383B (en) | Electroluminescent organic material and preparation method thereof and organic electroluminescence device | |
| CN105384759B (en) | Aromatic heterocycle derivative and the organic light emitting diode device using the compound | |
| CN103524497B (en) | Bipolarity phosphorescence host compound, preparation method and application and electroluminescent device | |
| CN106986870B (en) | Organic electric-field color-changing device and Phen based compound for this device | |
| CN106188141B (en) | A kind of OLED material and its application | |
| CN106898709B (en) | A kind of red phosphorescent organic electroluminescence device | |
| CN108440525A (en) | A kind of derivative and its organic electroluminescence device | |
| WO2018166096A1 (en) | Organic light-emitting device and method for manufacturing same | |
| CN103904225B (en) | A kind of organic electroluminescence device with barrier layer | |
| CN115028626B (en) | Thermally-induced delayed fluorescent material and preparation method and application thereof | |
| CN106366083A (en) | OLED material containing azocarbazole and phenanthroline structure, preparation method and application thereof | |
| CN102757451A (en) | Electron transport material and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to an organic electroluminescent material containing 4,5-diazazaspiro thioanthracene structure and its application and device Effective date of registration: 20211202 Granted publication date: 20180724 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220823 Granted publication date: 20180724 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |