CN109776393A - A kind of organic electroluminescence device of organic luminescent compounds and preparation method and the compound - Google Patents
A kind of organic electroluminescence device of organic luminescent compounds and preparation method and the compound Download PDFInfo
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- CN109776393A CN109776393A CN201910184076.7A CN201910184076A CN109776393A CN 109776393 A CN109776393 A CN 109776393A CN 201910184076 A CN201910184076 A CN 201910184076A CN 109776393 A CN109776393 A CN 109776393A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 57
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000010410 layer Substances 0.000 claims description 88
- 125000003118 aryl group Chemical group 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 125000001072 heteroaryl group Chemical group 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000005416 organic matter Substances 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 229940125904 compound 1 Drugs 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- -1 cyano, carboxyl Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 150000001721 carbon Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
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- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
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- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
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- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000284 extract Substances 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
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- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
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- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 claims description 3
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- NNCQYSGGLDLTSA-UHFFFAOYSA-N 4-phenyl-4H-1,2-benzothiazine Chemical compound C1=CC=C(C=C1)C2C=NSC3=CC=CC=C23 NNCQYSGGLDLTSA-UHFFFAOYSA-N 0.000 claims description 3
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 claims description 3
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- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 3
- 229940126214 compound 3 Drugs 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 125000005561 phenanthryl group Chemical group 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
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- HHWXYUTWYDPACR-UHFFFAOYSA-N 1,4-diphenylquinoxaline Chemical compound C12=CC=CC=C2N(C=2C=CC=CC=2)C=CN1C1=CC=CC=C1 HHWXYUTWYDPACR-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004305 biphenyl Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- AELBZZMQJAJEJW-UHFFFAOYSA-N 1-bromo-9-phenylcarbazole Chemical compound BrC1=CC=CC(C2=CC=CC=C22)=C1N2C1=CC=CC=C1 AELBZZMQJAJEJW-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- LAITVYHZSHLTHC-UHFFFAOYSA-N C1(=CC=CC=C1)C1(CC=C(N)C=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 Chemical class C1(=CC=CC=C1)C1(CC=C(N)C=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 LAITVYHZSHLTHC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
The present invention relates to technical field of organic luminescence materials, and in particular to the organic electroluminescence device of a kind of organic luminescent compounds and preparation method and the compound.The present invention proposes the solution that arylamine and heterocycle are introduced to the position 9- of fluorenes.Hole injection capacity/transmittability, high power efficiency, long-life are obtained by introducing arylamine；Appropriate glass transition temperature is obtained by introducing heterocycle, to obtain good electroluminescent organic material.There is splendid current efficiency and power efficiency and long-life by organic electroluminescence device prepared by machine luminophor of the invention.The preparation method of organic luminescent compounds of the invention, reproducible, yield is high.
Description
Technical field
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of organic luminescent compounds and preparation method and the change
Close the organic electroluminescence device of object.
Background technique
El light emitting device (EL device) is automatic luminous device, the advantage is that it can provide wider visual angle, larger
Contrast ratio and the faster response time.
Organic EL element is the self-emission device that following principle is utilized: by applying electric field, utilizing what is injected by anode
Hole makes fluorescent substance shine with the recombination energy by cathode injected electrons.It has the following structure: anode, cathode and Jie
In organic matter layer between the two.In order to improve the efficiency and stability of organic EL element, organic material layer includes having difference
The multilayer of material, such as hole injection layer (HIL), hole transmission layer (HTL), luminescent layer, electron transfer layer (ETL) and electronics note
Enter layer (EIL).
In this Organic Light Emitting Diode, when applying voltage between the anode and cathode, hole from anode and
Electron injection organic material layer from cathode.The exciton of generation generates the light with specific wavelength when migrating to ground state.
The most important factor for determining the luminous efficiency in organic el device is luminescent material.Up to the present, fluorescent material
It has been widely used as luminescent material.However, in view of electroluminescent mechanism, since phosphor material is theoretically compared with fluorescent material
Luminous efficiency is set to enhance four (4) times, therefore the exploitation of phosphorescent light-emitting materials is widely studied.Iridium (III) complex compound is extensive
Ground is referred to as phosphorescence dopant material.Currently, 4 ,-two carbazoles of 4 '-N, N '-biphenyl (CBP), (2- naphthalene) anthracene of 9,10- bis- (ADN) etc.
It is widely used as known phosphorescent light body material.Although these materials provide good luminous feature, have with
Lower disadvantage: (1) due to its lower glass transition temperature and bad thermal stability, lead to the service life reduction of device.It (2) include phosphorus
The organic el device of light material of main part needs higher driving voltage.Meanwhile in order to improve the efficiency of organic el device and stabilization
Property, need it that there is the multilayer knot comprising hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer
Structure.Hole can be changed to the hole transport efficiency, luminous efficiency, service life etc. of luminescent layer in its hole-transporting layer.Therefore, using copper
Phthalocyanine (CuPc), 4,4 '-bis- [N- (1- naphthalene)-N- phenyl amino] biphenyl (NPB), N, N '-diphenyl-N, N '-bis- (3- methyl
Phenyl)-(1,1 '-biphenyl) -4,4 '-diamines (TPD) etc. are as hole mobile material.However, using organic EL of these materials
Device is problematic in terms of quantum efficiency and service life.
Summary of the invention
The invention solves in the prior art the technical issues of, a kind of organic luminescent compounds and preparation method and the chemical combination are provided
The organic electroluminescence device of object, by the compound of the present invention preparation organic electroluminescence device have splendid current efficiency and
Power efficiency and long-life.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
The present invention provides a kind of organic luminescent compounds, and structural formula is as follows:
In formula: Ar1And Ar2It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or without taking
The C6-C30 aryl in generation or the 3-30 unit's heteroaryl for being substituted or being unsubstituted；Or connect with adjacent substituents to be formed monocycle or
The polycyclic aliphatic ring of C3-C30 or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
G ring indicate the C1-C30 naphthenic base for being substituted or being unsubstituted, the C6-C30 aryl that is substituted or is unsubstituted or
The 3-30 unit's heteroaryl for being substituted or being unsubstituted；
G ring may or may not exist；
X, Y, Z expression-O- ,-S- ,-SO in the absence of G ring2-、-C(R5)(R6)-、-N(R7)-、-Si(R5)(R6)-、-
Sn(R7)-or-Ge (R7)-；
X expression-the SO in the presence of G ring2-、-N(R7)-、-Si(R5)(R6)-、Sn(R7) or-Ge (R7)-；Y, Z indicate C,
N, O, S atom；The preferred phenyl ring of G ring, naphthalene nucleus, pyridine ring, 1- phenyl -1H- indoles, benzofuran, benzothiophene, 4- phenyl -4H-
Benzo [b] [1,4] oxazines, 4- phenyl -4H- benzothiazine, benzothiophene, 1,4- diphenyl -1,4- dihydro quinoxaline or 1,
1,4,4- tetramethyl-DHN 1,4 dihydronaphthalene；
R1To R4Hydrogen is each independently represented, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, is substituted or is unsubstituted
C1-C30 hydro carbons, the C1-C30 alkoxy for being substituted or being unsubstituted, the C3-C30 naphthenic base for being substituted or being unsubstituted, through taking
Generation or the C3-C30 cycloalkenyl being unsubstituted, are substituted or are unsubstituted the 3-7 membered heterocycloalkyl for being substituted or being unsubstituted
C6-C30 aryl, the 3-30 unit's heteroaryl for being substituted or being unsubstituted ,-NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15Or
Person-B (OR16)(OR17)；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or C3-C30 polycyclic aliphatic
Race's ring or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
R5To R17Hydrogen is each independently represented, the C1-C30 alkyl that is substituted or is unsubstituted, is substituted or is unsubstituted
C6-C30 aryl or 3 to 30 unit's heteroaryls that are substituted or are unsubstituted；Or connect with adjacent substituents to be formed be substituted or
The monocycle or C3-C30 multicyclic aliphatic ring or aromatic ring being unsubstituted；It is preferred that R7 is the benzene or methyl of benzene, cyano substitution；
A, b and d each independently represent integer 1 to 4；C indicates integer 1 to 3；It is preferred that a, b, c, d are 1.
It is preferred that Ar1And Ar2It each independently represents the C10-C25 aryl for being substituted or being unsubstituted or 13-25 member is miscellaneous
Aryl；Further preferred Ar1And Ar2Each independently represent the C14-C21 aryl for being substituted or being unsubstituted or 17-23 member
Heteroaryl；Further preferably Ar1And Ar2It each independently represents the C16-C19 aryl for being substituted or being unsubstituted or 19-21 member is miscellaneous
Aryl；Further preferred Ar1、Ar2For benzene, 1,1', 3', 1 "-triphenyl, even phenyl, diaminobenzene, phenanthryl, naphthalene, 1- phenyl
Naphthalene or 9,9- dimethyl fluorene.
It is preferred that any one of the organic luminescent compounds in following structures:
The present invention also provides a kind of preparation methods of organic luminescent compounds, comprising the following steps:
Step 1 is added after compound 2 and tetrahydrofuran in the reaction vessel, makes the container cold in a nitrogen atmosphere
But -78 DEG C are arrived, then n-BuLi is added dropwise in mixture, after stirring mixture at -78 DEG C, at room temperature by it
It is stirred, and is cooled to -78 DEG C；Hereafter, the compound 1 being dissolved in tetrahydrofuran is added dropwise in mixture；
After addition, reaction temperature is set to be warming up to room temperature, and stir mixture；Then aqueous ammonium chloride solution is added in reaction solution
To complete reaction, and reaction solution is extracted with ethyl acetate, then using the dry organic matter layer through extracting of magnesium sulfate, and
Using rotary evaporator remove solvent, with column chromatography purify surplus materials acquisition intermediate 1-1；
Step 2 after intermediate 1-1, compound 3 and methylene chloride are added in reaction vessel, is sufficiently displaced from nitrogen
Three times, the boron trifluoride ether being dissolved in methylene chloride is added dropwise in mixture for air；Mixing is stirred at room temperature
It after object, is quenched with distilled water, and mixture is extracted with dichloromethane；Then the organic matter layer extracted using sodium sulphate drying,
And solvent is removed using rotary evaporator, obtains intermediate 2 with column chromatography eluting surplus materials；
Step 3, by intermediate 2, Ar1Br and Ar2Br、Pd2(dba)3, P (t-Bu) 3, NaOt-Bu, toluene reacted；
Reaction with ether and water extracts organic matter after terminating, and organic layer dries later concentrated product silicagel column and again with magnesium sulfate
Method for crystallising obtains 1 compound of formula；
Its synthetic route is as follows:
In formula: Ar1And Ar2It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or without taking
The C6-C30 aryl in generation or the 3-30 unit's heteroaryl for being substituted or being unsubstituted；Or connect with adjacent substituents to be formed monocycle or
The polycyclic aliphatic ring of C3-C30 or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；G
Ring indicate the C1-C30 naphthenic base for being substituted or being unsubstituted, the C6-C30 aryl that is substituted or is unsubstituted or be substituted or
The 3-30 unit's heteroaryl being unsubstituted；G ring may or may not exist；In the absence of G ring X, Y, Z expression-O- ,-
S-、-SO2-、-C(R5)(R6)-、-N(R7)-、-Si(R5)(R6)-、-Sn(R7)-or-Ge (R7)-；The X expression-in the presence of G ring
SO2-、-N(R7)-、-Si(R5)(R6)-、Sn(R7) or-Ge (R7)-；Y, Z indicates C, N, O, S atom；R1To R4Each independently
Indicate hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, the C1-C30 hydro carbons for being substituted or being unsubstituted, be substituted or without
Substituted C1-C30 alkoxy, the C3-C30 naphthenic base for being substituted or being unsubstituted, the C3-C30 ring for being substituted or being unsubstituted
Alkenyl, the C6-C30 aryl for being substituted or being unsubstituted, is substituted or not the 3-7 membered heterocycloalkyl for being substituted or being unsubstituted
The 3-30 unit's heteroaryl that is substituted ,-NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15Or-B (OR16)(OR17)；Or with
Adjacent substituents connect to form the monocycle for being substituted or being unsubstituted or C3-C30 multicyclic aliphatic ring or aromatic ring, and carbon is former
The replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of son；R5To R17It each independently represents hydrogen, be substituted or without taking
The C1-C30 alkyl in generation, the C6-C30 aryl for being substituted or being unsubstituted or 3 to the 30 yuan of heteroaryls for being substituted or being unsubstituted
Base；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or C3-C30 multicyclic aliphatic ring or aromatic series
Ring；A, b and d each independently represent integer 1 to 4；C indicates integer 1 to 3；Hal is halogen.
The present invention also provides a kind of organic electroluminescence devices containing above-mentioned organic luminescent compounds.
In the above-mentioned technical solutions, the organic electroluminescence device includes:
First electrode, second electrode and the organic matter layer being placed between two electrode, wherein wrapped in the organic matter layer
Compound containing structure shown in formula 1；The compound of structure shown in formula 1 can be single form or be mixed with other materials
In organic matter layer.
In the above-mentioned technical solutions, the organic matter layer includes at least hole injection layer, hole transmission layer, both has hole
Injection is but also with hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and
Both had electron-transport but also with one or more of electron injection technical ability layer.
" organic matter layer " refers to disposing between organic electroluminescence device first electrode and second electrode in the present invention
The term of whole layers.
When the compound of 1 structure of formula is present in the luminescent layer in the organic matter layer, the compound of 1 structure of formula can
As light emitting host or to be entrained in other fluorescent hosts；
When the compound of 1 structure of formula is present in hole transmission layer or hole injection layer in the organic matter layer, institute
The compound for stating 1 structure of formula can be used as hole transmission layer, hole injection layer and both have hole injection and passes but also with hole
Defeated public affairs ergosphere.
Of the present invention includes that the device of the compound preparation of 1 structure of formula can be used for organic luminescent device
(OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or Organic Thin Film Transistors
(OTFT)。
Organic electroluminescence device of the present invention can pass through film vapor deposition, electron beam evaporation, physical vapour deposition (PVD)
The methods of on substrate evaporation metal and conductive oxide and they alloy formed anode, can also using rotation
Transfer film (spin-coating) or strip take the lead to be deposited；It can also be using molding (tape-casting), scraping blade method
(doctor-blading), silk-screen printing (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging)
The methods of reduce the number of plies manufacture.
The beneficial effects of the present invention are:
The present invention is provided to the hole mobile materials for solving the problems, such as traditional technology in organic el device.Traditional sky
Hole transport materials are substantially based on triaryl derivative.Although it is with cavity transmission ability and low driving voltage, in order to
It obtains suitable glass transition temperature and has to introduce a large amount of substituent group in its structure and promote its molecular weight.But this
Sample but reduces triplet energies or LUMO energy, so as to cause the deterioration of organic electroluminescence device.Ideal hole transport material
Material needs high glass transition temperature, Hole injection capacity and cavity transmission ability and suitable triplet energies and LUMO energy
Amount.Therefore, ideal material is obtained in order to solve the problems, such as conventional hole transmission material, the present invention is proposed to fluorenes
9- introduce the solution of arylamine and heterocycle.Hole injection capacity/transmittability, Gao Gong are obtained by introducing arylamine
Rate efficiency, long-life；Appropriate glass transition temperature is obtained by introducing heterocycle, to obtain good organic electroluminescent
Material.
By organic electroluminescence device prepared by machine luminophor of the invention there is splendid current efficiency and power to imitate
Rate and long-life.
The preparation method of organic luminescent compounds of the invention, reproducible, yield is high.
Specific embodiment
The present invention will the present invention will be described in detail by specific embodiment.It is intended to explain this however, being described below
Invention, and be not intended to limit the scope of the present disclosure in any way.
The present invention provides a kind of organic luminescent compounds, and structural formula is as follows:
In formula: Ar1And Ar2It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or without taking
The C6-C30 aryl in generation or the 3-30 unit's heteroaryl for being substituted or being unsubstituted；Or connect with adjacent substituents to be formed monocycle or
The polycyclic aliphatic ring of C3-C30 or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
G ring indicate the C1-C30 naphthenic base for being substituted or being unsubstituted, the C6-C30 aryl that is substituted or is unsubstituted or
The 3-30 unit's heteroaryl for being substituted or being unsubstituted；
G ring may or may not exist；
X, Y, Z expression-O- ,-S- ,-SO in the absence of G ring2-、-C(R5)(R6)-、-N(R7)-、-Si(R5)(R6)-、-
Sn(R7)-or-Ge (R7)-；
X expression-the SO in the presence of G ring2-、-N(R7)-、-Si(R5)(R6)-、Sn(R7) or-Ge (R7)-；Y, Z indicate C,
N, O, S atom；R3It connect to form the monocycle for being substituted or being unsubstituted or the polycyclic rouge of C3-C30 selected from hydrogen, or with adjacent substituents
Fat race ring or aromatic ring, the preferred phenyl ring of G ring, naphthalene nucleus, pyridine ring, 1- phenyl -1H- indoles, benzofuran, benzothiophene, 4-
Phenyl -4H- benzo [b] [1,4] oxazines, 4- phenyl -4H- benzothiazine, benzothiophene, 1,4- diphenyl -1,4- dihydro quinoline are disliked
Quinoline, 1,1,4,4- tetramethyl-DHN 1,4 dihydronaphthalene；
R1To R4Hydrogen is each independently represented, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, is substituted or is unsubstituted
C1-C30 hydro carbons, the C1-C30 alkoxy for being substituted or being unsubstituted, the C3-C30 naphthenic base for being substituted or being unsubstituted, through taking
Generation or the C3-C30 cycloalkenyl being unsubstituted, are substituted or are unsubstituted the 3-7 membered heterocycloalkyl for being substituted or being unsubstituted
C6-C30 aryl, the 3-30 unit's heteroaryl for being substituted or being unsubstituted ,-NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15Or
Person-B (OR16)(OR17)；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or C3-C30 polycyclic aliphatic
Race's ring or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
R5To R17Hydrogen is each independently represented, the C1-C30 alkyl that is substituted or is unsubstituted, is substituted or is unsubstituted
C6-C30 aryl or 3 to 30 unit's heteroaryls that are substituted or are unsubstituted；Or connect with adjacent substituents to be formed be substituted or
The monocycle or C3-C30 multicyclic aliphatic ring or aromatic ring being unsubstituted；It is preferred that R7 is the benzene of benzene, cyano substitution, methyl；
A, b and d each independently represent integer 1 to 4；C indicates integer 1 to 3；A, b and d each independently represents integer 1
To 4；C indicates integer 1 to 3；It is preferred that a, b, c, d are 1.
It is preferred that Ar1And Ar2It each independently represents the C10-C25 aryl for being substituted or being unsubstituted or 13-25 member is miscellaneous
Aryl；Further preferred Ar1And Ar2Each independently represent the C14-C21 aryl for being substituted or being unsubstituted or 17-23 member
Heteroaryl；Further preferably Ar1And Ar2It each independently represents the C16-C19 aryl for being substituted or being unsubstituted or 19-21 member is miscellaneous
Aryl；Further preferred Ar1、Ar2For benzene, 1,1':3', 1 "-triphenyl, even phenyl, diaminobenzene, phenanthryl, naphthalene, 1- phenyl
Naphthalene or 9,9- dimethyl fluorene.
Any one of the most preferably described organic luminescent compounds in following structures:
The present invention also provides a kind of preparation methods of organic luminescent compounds, comprising the following steps:
Step 1 is added after compound 2 and tetrahydrofuran in the reaction vessel, makes the container cold in a nitrogen atmosphere
But -78 DEG C are arrived, then n-BuLi is added dropwise in mixture, after stirring mixture at -78 DEG C, at room temperature by it
It is stirred, and is cooled to -78 DEG C；Hereafter, the compound 1 being dissolved in tetrahydrofuran is added dropwise in mixture；
After addition, reaction temperature is set to be warming up to room temperature, and stir mixture；Then aqueous ammonium chloride solution is added in reaction solution
To complete reaction, and reaction solution is extracted with ethyl acetate, then using the dry organic matter layer through extracting of magnesium sulfate, and
Using rotary evaporator remove solvent, with column chromatography purify surplus materials acquisition intermediate 1-1；
Step 2 after intermediate 1-1, compound 3 and methylene chloride are added in reaction vessel, is sufficiently displaced from nitrogen
Three times, the boron trifluoride ether being dissolved in methylene chloride is added dropwise in mixture for air；Mixing is stirred at room temperature
It after object, is quenched with distilled water, and mixture is extracted with dichloromethane；Then the organic matter layer extracted using sodium sulphate drying,
And solvent is removed using rotary evaporator, obtains intermediate 2 with column chromatography eluting surplus materials；
Step 3, by intermediate 2, Ar1Br and Ar2Br、Pd2(dba)3, P (t-Bu) 3, NaOt-Bu, toluene reacted；
Reaction with ether and water extracts organic matter after terminating, and organic layer dries later concentrated product silicagel column and again with magnesium sulfate
Method for crystallising obtains 1 compound of formula；
Its synthetic route is as follows:
In formula: Ar1And Ar2It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or without taking
The C6-C30 aryl in generation or the 3-30 unit's heteroaryl for being substituted or being unsubstituted；Or connect with adjacent substituents to be formed monocycle or
The polycyclic aliphatic ring of C3-C30 or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；G
Ring indicate the C1-C30 naphthenic base for being substituted or being unsubstituted, the C6-C30 aryl that is substituted or is unsubstituted or be substituted or
The 3-30 unit's heteroaryl being unsubstituted；G ring may or may not exist；In the absence of G ring X, Y, Z expression-O- ,-
S-、-SO2-、-C(R5)(R6)-、-N(R7)-、-Si(R5)(R6)-、-Sn(R7)-or-Ge (R7)-；The X expression-in the presence of G ring
SO2-、-N(R7)-、-Si(R5)(R6)-、Sn(R7) or-Ge (R7)-；Y, Z indicates C, N, O, S atom；R1To R4Each independently
Indicate hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, the C1-C30 hydro carbons for being substituted or being unsubstituted, be substituted or without
Substituted C1-C30 alkoxy, the C3-C30 naphthenic base for being substituted or being unsubstituted, the C3-C30 ring for being substituted or being unsubstituted
Alkenyl, the C6-C30 aryl for being substituted or being unsubstituted, is substituted or not the 3-7 membered heterocycloalkyl for being substituted or being unsubstituted
The 3-30 unit's heteroaryl that is substituted ,-NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15Or-B (OR16)(OR17)；Or with
Adjacent substituents connect to form the monocycle for being substituted or being unsubstituted or C3-C30 multicyclic aliphatic ring or aromatic ring, and carbon is former
The replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of son；R5To R17It each independently represents hydrogen, be substituted or without taking
The C1-C30 alkyl in generation, the C6-C30 aryl for being substituted or being unsubstituted or 3 to the 30 yuan of heteroaryls for being substituted or being unsubstituted
Base；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or C3-C30 multicyclic aliphatic ring or aromatic series
Ring；A, b and d each independently represent integer 1 to 4；C indicates integer 1 to 3；Hal is halogen.
It may include organic electroluminescent according to the present invention at least one of luminescent layer and hole transmission layer
Close object.
The present invention also provides a kind of organic electroluminescence devices containing above-mentioned organic luminescent compounds.
It is preferred that the organic electroluminescence device includes: first electrode, second electrode and is placed between two electrode
Organic matter layer, wherein the compound of the shown structure in the organic matter layer comprising at least one formula 1；The change of structure shown in formula 1
Closing object can be single form or is mixed in organic matter layer with other materials.
One in first and second electrode is anode, and the other is cathode.The organic matter layer includes to shine
Layer, and further include at least one be selected from hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, it is empty
The layer of the group of cave barrier layer and electronic barrier layer composition.
It is preferred that the organic matter layer includes at least hole injection layer, hole transmission layer, had both had hole injection but also with sky
Technical ability layer is transmitted in cave, electronic barrier layer, luminescent layer, hole blocking layer, and electron transfer layer and both has electronics biography at electron injecting layer
It is defeated but also with one or more of electron injection technical ability layer.
" organic matter layer " refers to disposing between organic electroluminescence device first electrode and second electrode in the present invention
The term of whole layers.
When the compound of 1 structure of formula is present in the luminescent layer in the organic matter layer, the compound of 1 structure of formula can
As light emitting host or to be entrained in other fluorescent hosts；
When the compound of 1 structure of formula is present in hole transmission layer or hole injection layer in the organic matter layer, institute
The compound for stating 1 structure of formula can be used as hole transmission layer, hole injection layer and both have hole injection and passes but also with hole
Defeated public affairs ergosphere.
Of the present invention includes that the device of the compound preparation of 1 structure of formula can be used for organic luminescent device
(OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or Organic Thin Film Transistors
(OTFT)。
Organic electroluminescence device of the present invention can pass through film vapor deposition, electron beam evaporation, physical vapour deposition (PVD)
The methods of on substrate evaporation metal and conductive oxide and they alloy formed anode, can also using rotation
Transfer film (spin-coating) or strip take the lead to be deposited；It can also be using molding (tape-casting), scraping blade method
(doctor-blading), silk-screen printing (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging)
The methods of reduce the number of plies manufacture.
The present invention relates to organic luminescent compounds of formula 1 and preparation method thereof, the organic electroluminescence hair comprising the compound
Optical device.
Embodiment 1: prepare compound 1
It is added after the bromo- 9- phenyl carbazole (60mmol) of 4- and 200mL tetrahydrofuran in the reaction vessel, in nitrogen atmosphere
Under so that the container is cooled to -78 DEG C.Then n-BuLi (2.5M, 60mmol) is slowly added dropwise in mixture.-
After being stirred mixture 30 minutes at 78 DEG C, it is stirred at room temperature 3 hours, and be cooled to -78 DEG C.Hereafter, it will be dissolved in
Fluorenone (60mmol) in 200mL tetrahydrofuran is slowly added dropwise in mixture.After addition, reaction temperature is made slowly to heat up
To room temperature, and stir mixture 16 hours.Then aqueous ammonium chloride solution is added in reaction solution to complete reaction, and
Reaction solution is extracted with ethyl acetate.Then using the dry organic matter layer through extracting of magnesium sulfate, and rotary evaporation is used
Device removes solvent.With column chromatography purify surplus materials obtain compound 1-1 (19.04g, 75%, mass spectrometry value: 423.42).
Reaction is added in compound 1-1 (45mmol), the deuterated aniline of 2,3,5,6- (46mmol) and 500L methylene chloride to hold
After in device, air is sufficiently displaced from three times with nitrogen, the boron trifluoride ether (46mmol) that will be dissolved in 100mL methylene chloride
Slowly it is added dropwise in mixture.It after mixture being stirred at room temperature 2 hours, is quenched with distilled water, and uses methylene chloride
Extract mixture.Then using the organic matter layer of the dry extraction of sodium sulphate, and solvent is removed using rotary evaporator.Use column
Chromatography purifying surplus materials acquisition compound 3-1 (41.85mmol, 93%, mass spectrometry value: 502.25).
By 27.2mmol compound 3-1 and 27.2mmol bromobenzene, Pd2(dba)3(2.64g,2.89mmol)、P(t-Bu)3
(1.17g, 5.78mmol), NaOt-Bu (16.7g, 173.5mmol), toluene 600mL are reacted under the conditions of 100 DEG C.Reaction
Organic matter, organic layer magnesium sulfate dry later concentrated product silicagel column and recrystallization are extracted with ether and water after terminating
Method obtains 18.22mmol compound 1 (67%), mass spectrometry value 654.32.
Embodiment 2: prepare compound 7
According to said synthesis route, referring to embodiment 1 method prepare compound 7 (yield=75% mass spectrometry value:
682.35)。
Embodiment 3: prepare compound 13
According to said synthesis route, referring to embodiment 1 method prepare compound 13 (yield=78% mass spectrometry value:
780.36)。
Embodiment 4: prepare compound 17
According to said synthesis route, referring to embodiment 1 method prepare compound 17 (yield=83% mass spectrometry value:
846.41)。
Embodiment 5: prepare compound 18
According to said synthesis route, referring to embodiment 1 method prepare compound 18 (yield=79% mass spectrometry value:
862.40)。
Embodiment 6: prepare compound 20
According to said synthesis route, referring to embodiment 1 method prepare compound 20 (yield=85% mass spectrometry value:
888.46)。
Embodiment 7: prepare compound 28
According to said synthesis route, referring to embodiment 1 method prepare compound 28 (yield=86% mass spectrometry value:
819.34)。
Embodiment 8: prepare compound 31
According to said synthesis route, referring to embodiment 1 method prepare compound 31 (yield=77% mass spectrometry value:
984.43)。
Embodiment 9: prepare compound 35
According to said synthesis route, referring to embodiment 1 method prepare compound 35 (yield=81% mass spectrometry value:
925.34)。
Embodiment 10: prepare compound 40
According to said synthesis route, referring to embodiment 1 method prepare compound 40 (yield=82% mass spectrometry value:
986.44)。
Embodiment 11: prepare compound 41
According to said synthesis route, referring to embodiment 1 method prepare compound 41 (yield=87% mass spectrometry value:
655.32)。
Embodiment 12: prepare compound 42
According to said synthesis route, referring to embodiment 1 method prepare compound 42 (yield=79% mass spectrometry value:
858.40)。
Embodiment 13: prepare compound 45
According to said synthesis route, referring to embodiment 1 method prepare compound 45 (yield=86% mass spectrometry value:
910.42)。
Embodiment 14: prepare compound 46
According to said synthesis route, referring to embodiment 1 method prepare compound 46 (yield=85% mass spectrometry value:
704.32)。
Embodiment 15: prepare compound 51
According to said synthesis route, referring to embodiment 1 method prepare compound 51 (yield=88% mass spectrometry value:
895.40)。
Embodiment 16: prepare compound 54
According to said synthesis route, referring to embodiment 1 method prepare compound 54 (yield=83% mass spectrometry value:
740.57)。
Embodiment 17: prepare compound 61
According to said synthesis route, referring to embodiment 1 method prepare compound 61 (yield=84% mass spectrometry value:
804.06)。
Embodiment 18: prepare compound 77
According to said synthesis route, referring to embodiment 1 method prepare compound 77 (yield=85% mass spectrometry value:
829.64)。
Embodiment 19: organic electroluminescence device of the manufacture containing compound 1
It is by coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic washing 30 minutes,
It is cleaned repeatedly with distilled water 2 times, ultrasonic washing 10 minutes, after distilled water cleans, isopropanol, acetone, methanol equal solvent
It is dry after ultrasonic washing in order, it is transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, vapor deposition is sent to
In machine.4,4', 4 "-three [the 2- naphthylphenyl amino] three for being 50nm by evaporation thickness on the ito transparent electrode having had been prepared for
Phenyl amine (2-TNATA) is used as hole injection layer.Then by compound 1 on the hole injection layer of formation vacuum evaporation thickness
For the hole transmission layer of 30nm.Then the blue material of main part 9 that evaporation thickness is 30nm on above-mentioned hole transmission layer, 10- bis-
(2- naphthalene) anthracene (ADN) and dopant material bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium (FIrpic).Main body material
The weight ratio of material and dopant material is 95:5.Then on above-mentioned luminescent layer vacuum evaporation with a thickness of 40nm TPBi as hole
Barrier layer and electron transfer layer.Vacuum evaporation is on above-mentioned electron transfer layer with a thickness of 0.5nm lithium fluoride (LiF), as electronics
Implanted layer.The aluminium that last evaporation thickness is 150nm completes the preparation of organic electroluminescence device with this as cathode.To
The performance characteristics of luminescence of the device arrived is tested, and measurement uses 2400 type source measuring unit of KEITHLEY, CS-2000 spectroradio
Luminance meter, to evaluate driving voltage, light emission luminance, luminous efficiency.
Embodiment 20: organic electroluminescence device of the manufacture containing compound 7
Compound 1 in embodiment 19 is replaced into compound 7, other methods are identical, and production contains the organic of compound 7
Electroluminescent device.
Embodiment 21: organic electroluminescence device of the manufacture containing compound 13
Compound 1 in embodiment 19 is replaced into compound 13, other methods are identical, make having containing compound 13
Organic electroluminescence devices.
Embodiment 22: organic electroluminescence device of the manufacture containing compound 17
Compound 1 in embodiment 19 is replaced into compound 17, other methods are identical, make having containing compound 17
Organic electroluminescence devices.
Embodiment 23: organic electroluminescence device of the manufacture containing compound 18
Compound 1 in embodiment 19 is replaced into compound 18, other methods are identical, make having containing compound 18
Organic electroluminescence devices.
Embodiment 24: organic electroluminescence device of the manufacture containing compound 20
Compound 1 in embodiment 19 is replaced into compound 20, other methods are identical, make having containing compound 20
Organic electroluminescence devices.
Embodiment 25: organic electroluminescence device of the manufacture containing compound 28
Compound 1 in embodiment 19 is replaced into compound 28, other methods are identical, make having containing compound 28
Organic electroluminescence devices.
Embodiment 26: organic electroluminescence device of the manufacture containing compound 31
Compound 1 in embodiment 19 is replaced into compound 31, other methods are identical, make having containing compound 31
Organic electroluminescence devices.
Embodiment 27: organic electroluminescence device of the manufacture containing compound 35
Compound 1 in embodiment 19 is replaced into compound 35, other methods are identical, make having containing compound 35
Organic electroluminescence devices.
Embodiment 28: organic electroluminescence device of the manufacture containing compound 40
Compound 1 in embodiment 19 is replaced into compound 40, other methods are identical, make having containing compound 40
Organic electroluminescence devices.
Embodiment 29: organic electroluminescence device of the manufacture containing compound 41
Compound 1 in embodiment 19 is replaced into compound 41, other methods are identical, make having containing compound 41
Organic electroluminescence devices.
Embodiment 30: organic electroluminescence device of the manufacture containing compound 42
Compound 1 in embodiment 19 is replaced into compound 42, other methods are identical, make having containing compound 42
Organic electroluminescence devices.
Embodiment 31: organic electroluminescence device of the manufacture containing compound 45
Compound 1 in embodiment 19 is replaced into compound 45, other methods are identical, make having containing compound 45
Organic electroluminescence devices.
Embodiment 32: organic electroluminescence device of the manufacture containing compound 46
Compound 1 in embodiment 19 is replaced into compound 46, other methods are identical, make having containing compound 46
Organic electroluminescence devices.
Embodiment 33: organic electroluminescence device of the manufacture containing compound 51
Compound 1 in embodiment 19 is replaced into compound 51, other methods are identical, make having containing compound 51
Organic electroluminescence devices.
Embodiment 34: organic electroluminescence device of the manufacture containing compound 54
Compound 1 in embodiment 19 is replaced into compound 54, other methods are identical, make having containing compound 54
Organic electroluminescence devices.
Embodiment 35: organic electroluminescence device of the manufacture containing compound 61
Compound 1 in embodiment 19 is replaced into compound 61, other methods are identical, make having containing compound 61
Organic electroluminescence devices.
Embodiment 36: organic electroluminescence device of the manufacture containing compound 77
Compound 1 in embodiment 19 is replaced into compound 77, other methods are identical, make having containing compound 77
Organic electroluminescence devices.
Comparative example 1:
According to the method for embodiment 19, the material of hole transmission layer is replaced into N'- bis- (1- naphthalene)-N by compound 1,
N'- diphenyl-(1,1'- biphenyl) -4,4'- diamines (NPD).
Table 1 is the luminous spy of the compound of preparation of the embodiment of the present invention and the organic electroluminescence device of a-NPD preparation
Property test result.
Table 1
Compound provided by the invention can be regarded as from upper table suitable glass transition temperature, Organic Electricity prepared therefrom
The luminous efficiency of electroluminescence device and service life increase significantly relative to the organic electroluminescence device prepared by a-NPD.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of organic luminescent compounds, which is characterized in that its structural formula is as follows:
In formula: Ar1And Ar2It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or be unsubstituted
C6-C30 aryl or the 3-30 unit's heteroaryl for being substituted or being unsubstituted；Or it is connect with adjacent substituents and to form monocycle or C3-
The polycyclic aliphatic ring of C30 or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
G ring indicates the C1-C30 naphthenic base for being substituted or being unsubstituted, the C6-C30 aryl for being substituted or being unsubstituted or through taking
Generation or the 3-30 unit's heteroaryl being unsubstituted；
G ring may or may not exist；
X, Y, Z expression-O- ,-S- ,-SO in the absence of G ring2-、-C(R5)(R6)-、-N(R7)-、-Si(R5)(R6)-、-Sn
(R7)-or-Ge (R7)-；
X expression-the SO in the presence of G ring2-、-N(R7)-、-Si(R5)(R6)-、Sn(R7) or-Ge (R7)-；Y, Z indicate C, N, O,
S atom；
R1To R4Each independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, the C1- for being substituted or being unsubstituted
C30 hydro carbons, the C3-C30 naphthenic base for being substituted or being unsubstituted, is substituted the C1-C30 alkoxy for being substituted or being unsubstituted
Or be unsubstituted C3-C30 cycloalkenyl, be substituted or be unsubstituted 3-7 membered heterocycloalkyl, be substituted or be unsubstituted
C6-C30 aryl, the 3-30 unit's heteroaryl for being substituted or being unsubstituted ,-NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15Or
Person-B (OR16)(OR17)；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or C3-C30 polycyclic aliphatic
Race's ring or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
R5To R17Each independently represent hydrogen, the C1-C30 alkyl that is substituted or is unsubstituted, the C6- for being substituted or being unsubstituted
C30 aryl or 3 to 30 unit's heteroaryls for being substituted or being unsubstituted；Connect with adjacent substituents to be formed be substituted or without
Substituted monocycle or C3-C30 multicyclic aliphatic ring or aromatic ring；
A, b and d each independently represent integer 1 to 4；C indicates integer 1 to 3.
2. organic luminescent compounds according to claim 1, which is characterized in that Ar1And Ar2It each independently represents through taking
Generation or the C10-C25 aryl or 13-25 unit's heteroaryl being unsubstituted.
3. organic luminescent compounds according to claim 1, which is characterized in that Ar1And Ar2It each independently represents through taking
Generation or the C14-C21 aryl or 17-23 unit's heteroaryl being unsubstituted.
4. organic luminescent compounds according to claim 1, which is characterized in that Ar1And Ar2It each independently represents through taking
Generation or the C16-C19 aryl or 19-21 unit's heteroaryl being unsubstituted.
5. organic luminescent compounds according to claim 1, which is characterized in that Ar1、Ar2Each independently represent for benzene,
1,1', 3', 1 "-triphenyl, even phenyl, diaminobenzene, phenanthryl, naphthalene, 1- phenylnaphthalene or 9,9- dimethyl fluorene.
6. organic luminescent compounds according to claim 1, which is characterized in that a, b, c, d are 1.
7. organic luminescent compounds according to claim 1, which is characterized in that G ring is phenyl ring, naphthalene nucleus, pyridine ring, 1- benzene
Base -1H- indoles, benzofuran, benzothiophene, 4- phenyl -4H- benzo [b] [1,4] oxazines, 4- phenyl -4H- benzothiazine, benzene
Bithiophene, 1,4- diphenyl -1,4- dihydro quinoxaline or 1,1,4,4- tetramethyl-DHN 1,4 dihydronaphthalene.
8. organic luminescent compounds according to claim 1, which is characterized in that it is any one in following structures
It is a:
9. a kind of preparation method of organic luminescent compounds described in claim 1, which comprises the following steps:
Step 1 is added after compound 2 and tetrahydrofuran in the reaction vessel, make in a nitrogen atmosphere the container be cooled to-
78 DEG C, then n-BuLi is added dropwise in mixture, after stirring mixture at -78 DEG C, it is carried out at room temperature
Stirring, and it is cooled to -78 DEG C；Hereafter, the compound 1 being dissolved in tetrahydrofuran is added dropwise in mixture；Addition
Afterwards, so that reaction temperature is warming up to room temperature, and stir mixture；Then aqueous ammonium chloride solution is added in reaction solution with complete
At reaction, and reaction solution is extracted with ethyl acetate, then using the dry organic matter layer through extracting of magnesium sulfate, and uses
Rotary evaporator remove solvent, with column chromatography purify surplus materials acquisition intermediate 1-1；
Step 2 after intermediate 1-1, compound 3 and methylene chloride are added in reaction vessel, is sufficiently displaced from air with nitrogen
Three times, the boron trifluoride ether being dissolved in methylene chloride is added dropwise in mixture；After mixture is stirred at room temperature,
It is quenched with distilled water, and mixture is extracted with dichloromethane；Then using the organic matter layer of the dry extraction of sodium sulphate, and make
Solvent is removed with rotary evaporator, obtains intermediate 2 with column chromatography eluting surplus materials；
Step 3, by intermediate 2, Ar1Br and Ar2Br、Pd2(dba)3, P (t-Bu) 3, NaOt-Bu, toluene reacted；Reaction knot
Shu Yihou ether and water extract organic matter, organic layer magnesium sulfate dry later concentrated product silicagel column and recrystallization side
Method obtains 1 compound of formula；
Its synthetic route is as follows:
In formula: Ar1And Ar2It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or be unsubstituted
C6-C30 aryl or the 3-30 unit's heteroaryl for being substituted or being unsubstituted；Or it is connect with adjacent substituents and to form monocycle or C3-
The polycyclic aliphatic ring of C30 or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；G ring table
Show the C1-C30 naphthenic base for being substituted or being unsubstituted, the C6-C30 aryl that is substituted or is unsubstituted or be substituted or without
Substituted 3-30 unit's heteroaryl；G ring may or may not exist；In the absence of G ring X, Y, Z expression-O- ,-S- ,-
SO2-、-C(R5)(R6)-、-N(R7)-、-Si(R5)(R6)-、-Sn(R7)-or-Ge (R7)-；The X expression-in the presence of G ring
SO2-、-N(R7)-、-Si(R5)(R6)-、Sn(R7) or-Ge (R7)-；Y, Z indicates C, N, O, S atom；R1To R4Each independently
Indicate hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, the C1-C30 hydro carbons for being substituted or being unsubstituted, be substituted or without
Substituted C1-C30 alkoxy, the C3-C30 naphthenic base for being substituted or being unsubstituted, the C3-C30 ring for being substituted or being unsubstituted
Alkenyl, the C6-C30 aryl for being substituted or being unsubstituted, is substituted or not the 3-7 membered heterocycloalkyl for being substituted or being unsubstituted
The 3-30 unit's heteroaryl that is substituted ,-NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15Or-B (OR16)(OR17)；Or with
Adjacent substituents connect to form the monocycle for being substituted or being unsubstituted or C3-C30 multicyclic aliphatic ring or aromatic ring, and carbon is former
The replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of son；R5To R17It each independently represents hydrogen, be substituted or without taking
The C1-C30 alkyl in generation, the C6-C30 aryl for being substituted or being unsubstituted or 3 to the 30 yuan of heteroaryls for being substituted or being unsubstituted
Base；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or C3-C30 multicyclic aliphatic ring or aromatic series
Ring；A, b and d each independently represent integer 1 to 4；C indicates integer 1 to 3；Hal is halogen.
10. a kind of organic electroluminescence device containing organic luminescent compounds described in claim 1-8 any one.
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| PCT/CN2019/078284 WO2020073605A1 (en) | 2018-10-11 | 2019-03-15 | Organic luminescent compound, preparation method therefor and organic electroluminescent device containing same |
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| CN114369055A (en) * | 2021-12-21 | 2022-04-19 | 武汉尚赛光电科技有限公司 | Organic compound and organic electroluminescent device comprising same |
| CN114394929A (en) * | 2022-01-25 | 2022-04-26 | 长春海谱润斯科技股份有限公司 | Carbazole-based triarylamine derivative and organic electroluminescent device thereof |
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Application publication date: 20190521 |