CN109206431A - Organic electroluminescent compounds and its application and organic electroluminescence device - Google Patents

Organic electroluminescent compounds and its application and organic electroluminescence device Download PDF

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CN109206431A
CN109206431A CN201810866667.8A CN201810866667A CN109206431A CN 109206431 A CN109206431 A CN 109206431A CN 201810866667 A CN201810866667 A CN 201810866667A CN 109206431 A CN109206431 A CN 109206431A
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CN109206431B (en
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吕瑶
冯美娟
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Green People's Science And Technology Ltd Co In Beijing
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Abstract

The present invention relates to organic electroluminescence device fields, disclose organic electroluminescent compounds and its application and organic electroluminescence device, which has structure shown in formula (I).Organic electroluminescent compounds provided by the invention can be improved the utilization rate of the exciton of organic electroluminescence device luminescent layer when in organic luminescent device especially as emitting layer material.Particularly, organic electroluminescent compounds of the invention being capable of blue light-emitting in organic electroluminescence device.

Description

Organic electroluminescent compounds and its application and organic electroluminescence device
Technical field
The present invention relates to organic electroluminescence device fields, and in particular to a kind of organic electroluminescent compounds, this is organic Application of the electroluminescent compounds in organic electroluminescence device a kind of contains one of the organic electroluminescent compounds Or the organic electroluminescence device of two or more compounds.
Background technique
Organic electroluminescent (OLED) technology compared to traditional liquid crystal technology for, without backlight irradiation and colour filter Device, pixel itself can shine and be presented on color display panel, also, possess superelevation contrast, super wide visible angle, reaction speed Fastly, low power consuming, curved surface, it is slim the features such as.
Organic electroluminescent is Dual Implantations type luminescent device, and electric energy is converted into the light of organic semiconducting materials molecule Energy.
Organic illuminating element generally comprise yin-yang the two poles of the earth and its between organic matter layer structure, organic matter layer is generally by sky Cave implanted layer, hole transmission layer, electronic barrier layer, luminescent layer, electron transfer layer, electron injecting layer are constituted.When to anode and yin When pole applies voltage, hole is injected from anode side luminescent layer, the lateral luminescent layer of cathode injects electronics, injected holes and electronics It is combined in luminescent layer and forms exciton, exciton shines when returning to ground state.
The performance of OLED is improved, most importantly raising luminous efficiency and stability.The performance of OLED is influenced, in particular, Each layer of material for forming OLED all has very important influence, such as base material, hole barrier to the performance of OLED Material, electron transport material, hole mobile material and electronics or exciton-blocking material, luminescent material etc..
Currently used each layer of material for forming OLED still has that driving voltage is high, service life is short, electric current effect Rate and the low defect of brightness, the especially efficiency of blue organic electroluminescent material and service life defect.
Summary of the invention
The purpose of the invention is to overcome aforementioned drawback of the existing technology, organic electroluminescence can be regulated and controled by providing one kind The HOMO energy level of luminescent material and the organic electroluminescent compounds of lumo energy, while can make containing the organic electroluminescent The electroluminescent organic material of compound has higher electron mobility and hole mobility, to improve luminous efficiency and bright Degree reduces driving voltage.
The present inventor has found under study for action, the organic electroluminescence provided by the invention with structure shown in formula (I) Luminophor has preferable thermodynamic stability, good film forming, suitable when being used as in electroluminescent organic material Triplet and energy gap, can significantly improve luminous efficiency and extend material service life.Accordingly, inventor completes Technical solution of the present invention.
To achieve the goals above, the first aspect of the present invention provides a kind of organic electroluminescent compounds, the compound With structure shown in formula (I),
In the structure shown in formula (I),
X is O or S；
Z is Si or C；
Y1、Y2、Y3、Y4、Y5、Y6、Y7And Y8In two atoms be N atom, remaining six atoms are C atom, and two N atom is non-conterminous；
R1And R2It is each independently selected from H, miscellaneous three cyclic group of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted contains Miscellaneous four cyclic group of nitrogen virtue, miscellaneous five cyclic group of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted hexichol amido and substituted At least one of phenyl；
R1And R2In the substituent group that is optionally present be each independently selected from C1-4Alkyl, phenyl, xenyl, dibenzofurans At least one of the carbazyl that base, dibenzothiophene, fluorenyl, carbazyl, hexichol amido and phenyl replace.
The second aspect of the present invention provides organic electroluminescent compounds described in aforementioned first aspect and sends out in organic electroluminescence Application in optical device.
The third aspect of the present invention provides a kind of containing in organic electroluminescent compounds described in aforementioned first aspect The organic electroluminescence device of one or more kinds of compounds.
Aforementioned organic electroluminescent compounds provided by the invention are in being used for organic luminescent device especially as luminous When layer material, the utilization rate of the exciton of organic electroluminescence device luminescent layer can be improved.Particularly, organic electroluminescence of the invention Luminophor being capable of blue light-emitting in organic electroluminescence device.
Technical solution of the present invention also has technical effect beneficial below: using organic electroluminescent chemical combination of the invention The organic electronic light emitting device of object can reduce driving voltage, improve luminous efficiency and prolong the service life.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the first aspect of the present invention provides a kind of organic electroluminescent compounds, which has formula (I) structure shown in,
In the structure shown in formula (I),
X is O or S；
Z is Si or C；
Y1、Y2、Y3、Y4、Y5、Y6、Y7And Y8In two atoms be N atom, remaining six atoms are C atom, and two N atom is non-conterminous；
R1And R2It is each independently selected from H, miscellaneous three cyclic group of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted contains Miscellaneous four cyclic group of nitrogen virtue, miscellaneous five cyclic group of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted hexichol amido and substituted At least one of phenyl；
R1And R2In the substituent group that is optionally present be each independently selected from C1-4Alkyl, phenyl, xenyl, dibenzofurans At least one of the carbazyl that base, dibenzothiophene, fluorenyl, carbazyl, hexichol amido and phenyl replace.
" C in the present invention1-4Alkyl " include methyl, ethyl, n-propyl, isopropyl, normal-butyl and tert-butyl.
Under preferable case, the nitrogenous miscellaneous tricyclic of virtue in substituted or unsubstituted nitrogenous miscellaneous three cyclic group of virtue is formula (a1) Or tricyclic shown in formula (a2), and in tricyclic shown in formula (a1) and formula (a2) arbitrarily can at key connection position and formula (I) In parent nucleus be keyed by C-C key or C-N；
Wherein, the Y in formula (a2) is O, S, C or N atom；
And C atom in tricyclic shown in formula (a1) and formula (a2) and/or N atom are optionally by being selected from C1-4Alkyl, benzene In the carbazyl that base, xenyl, dibenzofuran group, dibenzothiophene, fluorenyl, carbazyl, hexichol amido and phenyl replace At least one group replace；
Preferably, the nitrogenous miscellaneous Fourth Ring of virtue in substituted or unsubstituted nitrogenous miscellaneous four cyclic group of virtue of the invention is selected from Fourth Ring shown in formula (b1) and/or formula (b2),
And the C atom in Fourth Ring shown in formula (b1) and formula (b2) is optionally by being selected from C1-4Alkyl, in phenyl and xenyl At least one group replace.
Under preferable case, the nitrogenous miscellaneous five rings of virtue in substituted or unsubstituted nitrogenous miscellaneous five cyclic group of virtue is selected from formula Five rings shown in (c1) to formula (c12),
And X of the formula (c1) into formula (c12)1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11And X12It is each independently selected from O, S, C and N atom；
And C atom in five rings shown in formula (c1) to formula (c2) and/or N atom are optionally by being selected from C1-4Alkyl and At least one of phenyl group replaces；
According to a kind of preferred embodiment, structure shown in the formula (I) is following formula (I1) to formula (I5) institute At least one of structure shown:
And in the structure shown in formula (I1) to formula (I5), R1、R2, X and Z definition can be with foregoing teachings of the present invention In definition correspond to it is identical.
Several preferred embodiments of the invention presented below.
Specific embodiment 1:
Structure shown in the formula (I) is formula (I1) compound represented
And in the structure shown in formula (I1), R1、R2, X and Z definition can be with the definition in foregoing teachings of the present invention Correspondence is identical.
Specific embodiment 2:
Structure shown in the formula (I) is the particular compound enumerated in preferred additional technical feature in claim 3 In any one.
Specific embodiment 3:
Structure shown in the formula (I) is formula (I2) compound represented:
And in the structure shown in formula (I2), R1、R2, X and Z definition can be with the definition in foregoing teachings of the present invention Correspondence is identical.
Specific embodiment 4:
Structure shown in the formula (I) is the particular compound enumerated in preferred additional technical feature in claim 4 In any one.
Specific embodiment 5:
Structure shown in the formula (I) is formula (I3) compound represented:
And in the structure shown in formula (I3), R1、R2, X and Z definition can be with the definition in foregoing teachings of the present invention Correspondence is identical.
Specific embodiment 6:
Structure shown in the formula (I) is the particular compound enumerated in preferred additional technical feature in claim 5 In any one.
Specific embodiment 7:
Structure shown in the formula (I) is formula (I4) compound represented:
And in the structure shown in formula (I4), R1、R2, X and Z definition can be with the definition in foregoing teachings of the present invention Correspondence is identical.
Specific embodiment 8:
Structure shown in the formula (I) is the particular compound enumerated in preferred additional technical feature in claim 6 In any one.
Specific embodiment 9:
Structure shown in the formula (I) is formula (I5) compound represented:
And in the structure shown in formula (I5), R1、R2, X and Z definition can be with the definition in foregoing teachings of the present invention Correspondence is identical.
Specific embodiment 10:
Structure shown in the formula (I) is the particular compound enumerated in preferred additional technical feature in claim 7 In any one.
Specific embodiment 11:
Structure shown in the formula (I) is any one in the particular compound enumerated in claim 8.
There is no particular limitation for synthetic method of the present invention to the organic electroluminescent compounds of offer, those skilled in the art The preparation method of the structural formula combination preparation example for the organic electroluminescent compounds that member can provide according to the present invention determines suitable Synthetic method.
Further, the preparation side of some organic electroluminescent compounds is illustratively given in preparation example of the invention Method, those skilled in the art can obtain organic electroluminescence provided by the invention according to the preparation method of these illustrative preparation examples Luminophor.This will not be detailed here prepares the specific preparation methods of various compounds of the invention, art technology by the present invention Personnel should not be construed as limiting the invention.
The second aspect of the present invention provides organic electroluminescent compounds described in aforementioned first aspect and sends out in organic electroluminescence Application in optical device.
The third aspect of the present invention provides a kind of containing in organic electroluminescent compounds described in aforementioned first aspect The organic electroluminescence device of one or more kinds of compounds.
Preferably, the organic electroluminescent compounds are present in the electron transfer layer of the organic electroluminescence device, hair In at least one layer in photosphere and hole blocking layer.
Under preferable case, the organic electroluminescent compounds are present in the luminescent layer of the organic electroluminescence device.
Preferably, luminescent layer of the organic electroluminescent compounds as the organic electroluminescence device.
Preferably, the organic electroluminescent compounds are as the material of main part in the luminescent layer.
It is also derivative containing anthracene derivative, carbazoles in the material of main part in the luminescent layer under preferable case Object, fluorene kind derivative, aromatic amino-derivative, organic silicon derivative, carbazole-triazine derivative, in phosphorus oxygen base class derivative At least one compound.
Preferably, the anthracene derivative has general formula as follows:
Preferably, the phosphorus oxygen base class derivative has general formula as follows:
In the general formula of aforementioned anthracene derivative and phosphorus oxygen base class derivative, R11、R12、R13、R14、R15And R16It is respectively independent Ground is selected from singly-bound, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, fluorenes, click Azoles, thiophene, benzothiophene, dibenzothiophenes, furans, benzofuran, dibenzofurans, indoles, indole carbazole, indeno carbazole, Pyridine, pyrimidine, imidazoles, thiazole, quinoline, isoquinolin, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine, and Their substituent.
Preferably, guest materials is also contained in the luminescent layer, the guest materials is via phosphorescence, fluorescence, TADF (heat Activate delayed fluorescence), MLCT (metal to ligand charge shift), HLCT (there is hydridization CT state) and triplet state-triplet state elimination The compound for the transmitting that at least one of method method generates.
Preferably, the guest materials is selected from derivative, the derivative of anthracene, the derivative of pyrene, fluorene kind derivative, two Styryl virtue analog derivative, aromatic amino-derivative, organic silicon derivative, organic boron analog derivative, carbazole-triazines are derivative Object, Acridine derivatives, containing in ketones derivant, sulfuryl analog derivative, cyano derivative and oxa anthracenes derivative extremely Few one kind.
Preferably, the pyrene analog derivative has general formula as follows:
Preferably, the sulfuryl analog derivative has general formula as follows:
Preferably, the ketone group analog derivative has general formula as follows:
In the general formula of aforementioned pyrene analog derivative, sulfuryl analog derivative and ketone group analog derivative, R17、R18、R19、R20、R21、 R22And R23Be each independently selected from singly-bound, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, Benzophenanthrene, pyrene, fluorenes, carbazole, thiophene, benzothiophene, dibenzothiophenes, furans, benzofuran, dibenzofurans, indoles, indoles Carbazole, pyridine, pyrimidine, imidazoles, thiazole, quinoline, isoquinolin, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, is rattled away at indeno carbazole Piperazine or triazine and their substituent.
According to a kind of preferred embodiment, the organic electroluminescence device includes the base being cascading Plate, anode, hole injection layer (HIL), hole transmission layer (HTL), optional electronic barrier layer, luminescent layer (EML), optional sky Cave barrier layer, electron transfer layer (ETL), electron injecting layer (EIL) and cathode.
Preferably, the first coating and/or the second coating are also contained in the organic electroluminescence device, described first covers The outer surface of the anode is arranged in cap rock and the outer surface of the cathode is arranged in second coating.
Such as the organic electroluminescence device can be cascading the first coating, anode, hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), luminescent layer (EML), hole blocking layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL), cathode and the second coating.
Under preferable case, contain first party of the present invention in first coating and second coating each independently Organic compound described in face.
Glass substrate, plastic or metal substrate can be used in the substrate of the invention.
Preferably, the anode material for forming the anode is selected from one of tin indium oxide, indium zinc oxide and stannic oxide Or it is a variety of.Wherein, the thickness for the anode active layer which forms for example can be 100-1700 angstroms.
Preferably, the material for forming the hole injection layer is hole-injecting material, and forms the hole transmission layer Material be that hole mobile material and the hole-injecting material and hole mobile material are selected from aromatic amine derivative (example Such as NPB, SqMA1), six azepine triphenylenes (such as HACTN), indolocarbazole derivatives, conducting polymer (such as PEDOT/PSS), phthalocyanine or derivatives of porphyrin, dibenzo indeno fluorenamine, two fluorenamine of spiral shell.
The aromatic amine that following general formula for example can be used in the hole injection layer (HIL) and hole transmission layer (HTL) is derivative Object is formed:
The group of R1 to R9 in above-mentioned general formula is each independently selected from singly-bound, hydrogen, deuterium, alkyl, benzene, biphenyl, three Benzene, naphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, fluorenes, dimethyl fluorene, two fluorenes of spiral shell, carbazole, thiophene, benzothiophene, dibenzothiophenes, furans, Benzofuran, dibenzofurans, indoles, indole carbazole, indeno carbazole, pyridine, pyrimidine, imidazoles, thiazole, quinoline, isoquinolin, quinoline Quinoline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine.
Preferably, hole injection layer is with a thickness of 100-2000 angstroms, and more preferably 200-600 angstroms.
Preferably, thickness of hole transport layer is 100-1000 angstroms, more preferably 200-400 angstroms.
Preferably, the material for forming the electron transfer layer can also be selected from metal complex, benzimidizole derivatives, phonetic At least one of piperidine derivatives, pyridine derivate, quinoline and quinoxaline derivant substance.Preferably, the electronics Transport layer with a thickness of 100-600 angstroms.
The forming material of the electronic barrier layer is not particularly limited, under normal circumstances, can have the following 1st or/and The compound of 2nd condition is contemplated that use:
1st: having higher lumo energy, purpose is exactly to reduce the number of electrons for leaving luminescent layer, to improve electricity The recombination probability of son and hole in luminescent layer.
2nd: having biggish triplet energy state, purpose is exactly to reduce the exciton quantity for leaving luminescent layer, to improve The luminous efficiency of exciton conversion.
The material for forming the electronic barrier layer includes but is not limited to aromatic amine derivative (such as NPB), two fluorenamine of spiral shell (such as SpMA2), part of electron-blocking materials are similar with the structure of hole mobile material with hole-injecting material.It is preferred that electricity Sub- barrier layer with a thickness of 50-600 angstroms.
The material for forming the hole blocking layer is preferably the compound for having following 1st and/or the 2nd condition:
1st: having higher HOMO energy level, purpose is exactly to reduce the hole number for leaving luminescent layer, to improve electricity The recombination probability of son and hole in luminescent layer.
2nd: having biggish triplet energy state, purpose is exactly to reduce the exciton quantity for leaving luminescent layer, to improve The luminous efficiency of exciton conversion.
The material for forming the hole blocking layer for example can also be containing ferrosin derivative (such as Bphen, BCP), benzene And phenanthrene derivative, benzimidizole derivatives.Preferably, the hole blocking layer with a thickness of 50-600 angstroms.
Preferably, the electron injecting layer material is LiF, Al2O3, one of MnO etc. or a variety of.Preferably, electronics is infused Enter layer with a thickness of 1-50 angstroms.
Preferably, the cathode material is one of Al, Mg and Ag or a variety of.Preferably, cathode layer with a thickness of 800-1500 angstroms.
Organic electroluminescence device of the invention is coated with a layer or multiple layers preferably by means of sublimation method.This In the case of, in vacuum sublimation system, less than 10-3Pa, preferably smaller than 10-6It is applied under the initial pressure of Pa by vapor deposition Add compound provided by the invention.
Organic electroluminescence device of the invention preferably by organic vapor phase deposition method or by means of carrier gas distillation come It is coated with a layer or multiple layers.In this case, 10-6Apply the material under the pressure of Pa to 100Pa.This method Special example is organic vapor deposition jet printing method, wherein compound provided by the invention directly applies by nozzle and forms device Structure.
Organic electroluminescence device of the invention is preferably by light-initiated thermal imaging or thermal transfer, to form one layer or more Layer structure.
The compound of the present invention is preferably configured to solution by organic electroluminescence device of the invention, by spin coating or by In any mode of printing, such as silk-screen printing, flexible version printing, ink jet printing, lithographic printing, more preferably ink jet printing, To form a layer or multiple layers of structure.But it when making multiple layers, is easy to appear between layers in this way Destroy, i.e., when complete a layer when, then when making another layer with solution, the solvent in solution can destroy shape At layer, this is unfavorable for element manufacturing.Compound provided by the invention can be replaced by structural modification, allow chemical combination of the invention Object crosslinks effect in the case where heating or uv-exposure, to keep complete layer without being destroyed.The present invention Compound in addition can apply from solution, and by subsequent being crosslinked in polymer network or be fixed on corresponding In layer.
Preferably, by applying one or more layer from solution and applying one or more layer by sublimation method To manufacture organic electroluminescence device of the invention.
The preferred solvent for preparing organic electroluminescence device of the invention is selected from toluene, methyl phenyl ethers anisole, ortho-xylene, two Toluene, paraxylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, benzene Oxygroup toluene, especially 3- phenoxytoluene, 1,2,3,5- durols, 1,2,4,5- durols, 1- methyl naphthalene, 2- methyl Benzothiazole, 2- phenoxetol, 2-Pyrrolidone, 3- methylanisole, 4- methylanisole, 3,4- dimethylanisole, 3,5- dimethylanisole, acetophenone, benzothiazole, butyl benzoate, isopropanol, isopropylbenzene, cyclohexanol, cyclohexanone, hexamethylene Base benzene, decahydronaphthalene, detergent alkylate, methyl benzoate, NMP, and base benzene, phenetole, 1,4- diisopropyl benzene, two different to methyl Benzyl oxide, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ethers, Diethylene glycol monobutyl ether, tripropylene glycol dimethyl, tetraethylene glycol dimethyl ether, 2- isopropyl naphthalene, penta benzene, own benzene, benzene in heptan, Bis- (3, the 4- 3,5-dimethylphenyl) ethane of pungent benzene, 1,1-, 2- enanthol, 3- enanthol or these solvents mixture.
Preferably, when preparing organic electroluminescence device of the invention, by the compound of the present invention and other compounds It is first sufficiently mixed, then again by above-mentioned applying mode, to form a layer or multiple layers.It is more preferable that in vacuum In sublimation system, less than 10-3Pa, preferably smaller than 10-6Under the initial pressure of Pa, each compound is applied by vapor deposition, is come Form a layer or multiple layers.
Technical solution of the present invention is described in detail below by way of specific example.
In case of no particular description, the various raw materials used are all from commercially available.
Preparation example 1: prepare compound 1-1
The synthesis of intermediate 1-1-1: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds Benzofuran -3- the boric acid of 0.1mol, the adjacent bromo-iodobenzene of 0.1mol, the potassium carbonate of 0.25mol, the ferrocene dichloro of 0.001mol Change palladium, stirring is warming up to reflux, detects raw material end of reaction after 4h, reaction solution decompression is spin-dried for, chromatographs to obtain centre by column Body 1-1-1 (yield 71%).
The synthesis of intermediate 1-1-2: the intermediate 1-1-1 of 0.071mol is dissolved in 200ml tetrahydro furan in there-necked flask In muttering, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.071mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-1-2 (yield 50%).
The synthesis of intermediate 1-1-3: 0.035mol intermediate 1-1-2 is added in 130mlTHF and is stirred, is cooled to -78 DEG C, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, heat preservation is warmed to room temperature after 30 minutes, 2h is then kept the temperature at room temperature, - 78 DEG C are cooled to, the Br2 of 0.035mol is then added, is warmed to room temperature again after completion of dropwise addition.Raw material is detected after 5h to have reacted Finish, water 250ml is added dropwise into reaction solution, organic phase is obtained by extraction and is spin-dried for, chromatographs to obtain intermediate 1-1-3 (yield by column 48%).
The synthesis of compound 1-1: the intermediate 1-3 of 0.017mol is dissolved in 80ml toluene solvant, under nitrogen protection according to (two is sub- by the secondary carbazole that 0.017mol is added, 0.0425mol sodium tert-butoxide, 0.00017mol tri-tert-butylphosphine, 0.00017mol tri- Benzylacetone) two palladiums, stir and are warming up to back flow reaction, raw material end of reaction is detected after 4h, reaction solution decompression is spin-dried for, column is passed through Chromatography obtains 0.012mol compound 1-1 (yield 70%).
Calculated value C37H21N3O:523.58 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.25~7.33 (7H, m), 7.48~7.49 (4H, m), 7.63~7.67 (2H, m), 7.89~7.94 (2H, m), 8.12~ 8.13 (1H, m), 8.51~8.55 (3H, m).
Preparation example 2: prepare compound 1-6
The synthesis of intermediate 1-6-1: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds The 3- boric acid benzofuran of 0.1mol, chloro- 2 iodobenzene of the bromo- 3- of the 1- of 0.1mol, the potassium carbonate of 0.25mol, two cyclopentadienyls of 0.001mol Iron palladium chloride, stirring are warming up to reflux, detect raw material end of reaction after 4h, reaction solution decompression is spin-dried for, is chromatographed by column To intermediate 1-6-1 (yield 71%).
The synthesis of intermediate 1-6-2: the intermediate 1-6-1 of 0.071mol is dissolved in 200ml tetrahydro furan in there-necked flask In muttering, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.071mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-6-2 (yield 50%).
The synthesis of compound 1-6: the intermediate 6-2 of 0.017mol is dissolved in 80ml toluene solvant, under nitrogen protection according to (two is sub- by the secondary carbazole that 0.017mol is added, 0.0425mol sodium tert-butoxide, 0.00017mol tri-tert-butylphosphine, 0.00017mol tri- Benzylacetone) two palladiums, stir and are warming up to back flow reaction, raw material end of reaction is detected after 4h, reaction solution decompression is spin-dried for, column is passed through Chromatography obtains compound 1-6 (yield 70%).
Calculated value C37H21N3O:523.58 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.20~7.48 (10H, m), 7.63~7.66 (2H, m), 7.89~7.97 (3H, m), 8.12~8.12 (1H, m), 8.51 ~8.55 (3H, m).
Preparation example 3: prepare compound 1-17
The synthesis of intermediate 1-17-1: the 2- bromine carbazole of 0.01mol is dissolved in 20ml dioxane solvent, is protected in nitrogen 9- phenyl carbazole -3- boric acid, 0.025mol potassium acetate, the bis- (hexichol of 0.0001mol 1,1 '-of 0.01mol are sequentially added under shield Base phosphine) ferrocene palladium chloride, it stirs and is warming up to back flow reaction, raw material end of reaction is detected after 4h, reaction solution decompression is spin-dried for, Intermediate 1-17-1 (yield 80%) is chromatographed to obtain by column.
The synthesis of compound 1-17: synthetic method obtains compound 1-17 (yield 70%) with the synthesis of compound 1-1.
Calculated value C55H32N4O:764.87 ± 1.δ=7.00~7.60 1H-NMR (400MHz, CDCl3) (ppm) (28H, M), 7.77~7.78 (2H, m), 8.57~8.58 (2H, m).
Preparation example 4: prepare compound 1-22
The synthesis of intermediate 1-22-1: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds The 3- boric acid benzofuran of 0.1mol, chloro- 1 iodobenzene of the bromo- 4- of the 2- of 0.1mol, the potassium carbonate of 0.25mol, two cyclopentadienyls of 0.001mol Iron palladium chloride, stirring are warming up to reflux, detect raw material end of reaction after 4h, reaction solution decompression is spin-dried for, is chromatographed by column To compound 1-22-1 (yield 75%).
The synthesis of intermediate 1-22-2: the intermediate 1-22-1 of 0.075mol is dissolved in 200ml tetrahydro in there-necked flask In furans, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.075mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-22-2 (yield 53%).
The synthesis of compound 1-22: the intermediate 1-22-2 of 0.04mol is dissolved in 80ml toluene solvant, under nitrogen protection Sequentially add 11H- benzo carbazole, the 0.1mol sodium tert-butoxide, 0.004mol tri-tert-butylphosphine, 0.004mol tri- (two of 0.04mol BENZYLIDENE ACETONE) two palladiums, stir and are warming up to back flow reaction, raw material end of reaction is detected after 4h, reaction solution decompression is spin-dried for, is passed through Column chromatographs to obtain compound 1-22 (yield 62.5%).
Calculated value C41H23N3O:573.64 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.25~7.38 (4H, m), 7.48~7.67 (9H, m), 7.89~7.94 (2H, m), 8.12~8.16 (2H, m), 8.51~ 8.55 (4H, m).
Preparation example 5: prepare compound 1-31
The synthesis of compound 1-31: the intermediate 1-1-3 of 0.01mol is dissolved in 70ml toluene solvant, under nitrogen protection Sequentially add the thiophene piperazine, 0.025mol sodium tert-butoxide, 0.0001mol tri-tert-butylphosphine, (two Asias 0.0001mol tri- of 0.01mol Benzylacetone) two palladiums, stir and are warming up to back flow reaction, raw material end of reaction is detected after 4h, reaction solution decompression is spin-dried for, column is passed through Chromatography obtains compound 1-31 (yield 68%).
Calculated value C37H21N3OS:555.65 ± 1.δ=6.4~6.41 1H-NMR (400MHz, CDCl3) (ppm) (1H, M), 6.68~6.75 (4H, m), 6.8~7.13 (11H, m), 7.36~7.37 (1H, m), 7.60~7.61 (2H, m), 8.57~ 8.58 (2H, m).
Preparation example 6: prepare compound 1-39
The synthesis of compound 1-39: the intermediate 1-1-3 of 0.017mol is dissolved in 80ml toluene solvant, under nitrogen protection Sequentially add the 11- phenyl -11,12- indoline of 0.017mol simultaneously [2,3-a] carbazole, 0.0425mol sodium tert-butoxide, 0.00017mol tri-tert-butylphosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, examine after 4h Raw material end of reaction is surveyed, reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-39 (yield 70%) by column.
Calculated value C49H28N4O:688.77 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.25~7.33 (8H, m), 7.45~7.67 (10H, m), 7.89~7.94 (3H, m), 8.12~8.12 (1H, d), 8.51 ~8.55 (4H, m).
Preparation example 7: prepare compound 1-42
The synthesis of intermediate 1-42-1: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds The 3- boric acid benzofuran of 0.1mol, chloro- 2 iodobenzene of the bromo- 3- of the 1- of 0.01mol, the potassium carbonate of 0.025mol, 0.0001mol's Ferrocene palladium chloride, stirring are warming up to reflux, detect raw material end of reaction after 4h, reaction solution decompression is spin-dried for, column layer is passed through Analysis obtains intermediate 1-42-1 (yield 71%).
The synthesis of intermediate 1-42-2: the intermediate 1-42-1 of 0.071mol is dissolved in 200ml tetrahydro in there-necked flask In furans, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.071mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-42-2 (yield 50%).
The synthesis of compound 1-42: the intermediate 1-42-2 of 0.017mol is dissolved in 80ml toluene solvant, nitrogen protection Under sequentially add 11- phenyl -11,12- indoline [2,3-a] carbazole of 0.017mol, 0.0425mol sodium tert-butoxide, 0.00017mol tri-tert-butylphosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, examine after 4h Raw material end of reaction is surveyed, reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-42 (yield 70%) by column.
Calculated value C49H28N4O:688.77 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.25~7.66 (18H, m), 7.89~7.94 (3H, m), 8.12~8.12 (1H, d), 8.51~8.55 (4H, m).
Preparation example 8: prepare compound 1-46
The synthesis of compound 1-46: the intermediate 1-1-3 of 0.017mol is dissolved in 80ml toluene solvant, under nitrogen protection Sequentially add 5- phenyl -5,12- indoline [3,2-a] carbazole of 0.017mol, 0.0425mol sodium tert-butoxide, 0.00017mol tri-tert-butylphosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, examine after 4h Raw material end of reaction is surveyed, reaction solution decompression is spin-dried for, chromatographs to obtain 0.012mol compound 1-46 (yield 70%) by column.
Calculated value C49H28N4O:688.77 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.23~7.33 (9H, m), 7.45~7.67 (9H, m), 7.89~7.94 (3H, m), 8.12~8.12 (1H, d), 8.51~ 8.55 (4H, m).
Preparation example 9: prepare compound 1-47
The synthesis of intermediate 1-47-1: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds The 3- boric acid benzofuran of 0.1mol, chloro- 2 iodobenzene of the bromo- 3- of the 1- of 0.01mol, the potassium carbonate of 0.025mol, 0.0001mol's Ferrocene palladium chloride, stirring are warming up to reflux, detect raw material end of reaction after 4h, reaction solution decompression is spin-dried for, column layer is passed through Analysis obtains intermediate 1-47-1 (yield 71%).
The synthesis of intermediate 1-47-2: the intermediate 1-47-1 of 0.071mol is dissolved in 200ml tetrahydro in there-necked flask In furans, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.071mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-47-2 (yield 50%).
The synthesis of compound 1-47: the intermediate 1-47-2 of 0.017mol is dissolved in 80ml toluene solvant, nitrogen protection Under sequentially add 12- phenyl -5,12- indoline [3,2-a] carbazole of 0.017mol, 0.0425mol sodium tert-butoxide, 0.00017mol tri-tert-butylphosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, examine after 4h Raw material end of reaction is surveyed, reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-47 (yield 70%) by column.
Calculated value C49H28N4O:688.77 ± 1.δ=6.81~6.81 (2H, m) 1H-NMR (400MHz, CDCl3) (ppm), 7.23~7.66 (18H, m), 7.89~7.94 (3H, m), 8.12~8.12 (1H, d), 8.51~8.55 (4H, m).
Preparation example 10: prepare compound 1-50
The synthesis of intermediate 1-50-1: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds The 3- boric acid benzofuran of 0.1mol, the adjacent bromo-iodobenzene of 0.01mol, the potassium carbonate of 0.025mol, the ferrocene two of 0.0001mol Palladium chloride, stirring are warming up to reflux, and raw material end of reaction is detected after 4h, and reaction solution is depressurized and is spin-dried for, and chromatograph to obtain by column Mesosome 1-50-1 (yield 71%).
The synthesis of intermediate 1-50-2: the intermediate 1-50-1 of 0.071mol is dissolved in 200ml tetrahydro in there-necked flask In furans, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.071mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-50-2 (yield 50%).
The synthesis of intermediate 1-50-3: 0.035mol intermediate 1-50-2 is added in 130mlTHF and is stirred, is cooled to -78 DEG C, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, heat preservation is warmed to room temperature after 30 minutes, 2h is then kept the temperature at room temperature, - 78 DEG C are cooled to, 0.035molBr2 is then added, is warmed to room temperature again after completion of dropwise addition.Raw material end of reaction is detected after 5h, Water 250ml is added dropwise into reaction solution has a large amount of solids to be precipitated, and stirring half an hour is obtained by filtration during residue chromatographs to obtain by column Mesosome 1-50-3 (yield 48%).
The synthesis of compound 1-50: the intermediate 1-50-3 of 0.017mol is dissolved in 80ml toluene solvant, nitrogen protection Under sequentially add 8H- [1] benzothiophene of 0.017mol simultaneously [2,3-c] carbazole, 0.0425mol sodium tert-butoxide, 0.00017mol Tri-tert-butylphosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, detection raw material reaction after 4h It finishes, reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-50 (yield 70%) by column.
Calculated value C43H23N3OS:629.73 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.25~7.33 (6H, m), 7.44~7.67 (6H, m), 7.73~7.98 (5H, m), 8.51~8.55 (4H, m).
Preparation example 11: prepare compound 1-56
The synthesis of intermediate 1-56: being added the dioxane solvent of 165ml in there-necked flask, and 5ml water sequentially adds The 3- boric acid benzofuran of 0.1mol, the adjacent bromo-iodobenzene of 0.01mol, the potassium carbonate of 0.025mol, the ferrocene two of 0.0001mol Palladium chloride, stirring are warming up to reflux, and raw material end of reaction is detected after 4h, and reaction solution is depressurized and is spin-dried for, and chromatograph to obtain by column Mesosome 1-56 (yield 71%).
The synthesis of intermediate 1-56-2: the intermediate 1-56-1 of 0.071mol is dissolved in 200ml tetrahydro in there-necked flask In furans, -78 DEG C are cooled to, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, is put into thereto after 30 minutes 4, the 5- carboline -9- ketone of 0.071mol, temperature is warmed to room temperature, and then stirs gained mixture 1 hour.It is put into thereto The HCl (1N) of 200ml and by gained mixture stir 30 minutes after, by layer separate to remove solvent, then residue is used Re-crystallizing in ethyl acetate obtains intermediate 1-56-2 (yield 50%).
The synthesis of intermediate 1-56-3: 0.035mol intermediate 1-56-2 is added in 130mlTHF and is stirred, is cooled to -78 DEG C, the n-BuLi (2.5M) of 40ml is then added dropwise thereto, heat preservation is warmed to room temperature after 30 minutes, 2h is then kept the temperature at room temperature, - 78 DEG C are cooled to, 0.035molBr2 is then added, is warmed to room temperature again after completion of dropwise addition.Raw material end of reaction is detected after 5h, Water 250ml is added dropwise into reaction solution has a large amount of solids to be precipitated, and stirring half an hour is obtained by filtration during residue chromatographs to obtain by column Mesosome 1-56-3 (yield 8%).
The synthesis of compound 1-56: the intermediate 1-56-3 of 0.017mol is dissolved in 80ml toluene solvant, nitrogen protection Under sequentially add 5H- [1] benzothiophene of 0.017mol simultaneously [3,2-c] carbazole, 0.0425mol sodium tert-butoxide, 0.00017mol Tri-tert-butylphosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, detection raw material reaction after 4h It finishes, reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-56 (yield 70%) by column.
Calculated value C43H23N3OS:629.73 ± 1.δ=7.03~7.13 1H-NMR (400MHz, CDCl3) (ppm) (8H, M), 7.31~7.60 (10H, m), 7.78~7.86 (3H, m), 8.57~8.58 (2H, m).
Preparation example 12: prepare compound 1-61
The synthesis of compound 1-61: the intermediate 117-3 of 0.017mol is dissolved in 80ml toluene solvant, under nitrogen protection Sequentially add 5H- [1] benzofuran of 0.017mol simultaneously [3,2-c] carbazole, 0.0425mol sodium tert-butoxide, 0.00017mol tri- Tert-butyl phosphine, 0.00017mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, and detection raw material has reacted after 4h Finish, reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-61 (yield 70%) by column.
Calculated value C43H23N3O2:613.66 ± 1.δ=7.03~7.20 1H-NMR (400MHz, CDCl3) (ppm) (12H, m), 7.36~7.60 (9H, m), 8.57~8.58 (2H, m).
Preparation example 13: prepare compound 1-65
The synthesis of compound 1-65: the intermediate 1-1-3 of 0.01mol is dissolved in 70ml toluene solvant, under nitrogen protection Sequentially add 5,7- dihydro -7,7- dimethyl-indeno [2,1-b] carbazole of 0.01mol, 0.025mol sodium tert-butoxide, 0.0001mol tri-tert-butylphosphine, 0.0001mol tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, detect after 4h Reaction solution decompression is spin-dried for, chromatographs to obtain compound 1-65 (yield 68%) by column by raw material end of reaction.
Calculated value C46H29N3O:639.74 ± 1.δ=1.67~1.68 1H-NMR (400MHz, CDCl3) (ppm) (6H, D), 7.00~7.24 (10H, m) 7.36~7.61 (9H, m), 7.69~7.69 (1H, s), 8.06~8.07 (1H, m), 8.57~ 8.58 (2H, m).
Preparation example 14: prepare compound 2-73
The synthesis of intermediate 2-73-1: preparing grignard reagent, by the 3 of 0.01mol, 3 ' -2,2 '-bipyridyls, 0.4mol Magnesium is added in 30ml tetrahydrofuran, is warming up to back flow reaction initiation, is slowly dropped into the 3 of remaining 0.09mol, 3 ' -2,2 '-connection Pyridine tetrahydrofuran saturated solution heat preservation reflux 1h or so, nitrogen protection is spare.The four of 0.1mol is added in another there-necked flask Silicon chloride, tetrahydrofuran stir evenly, and nitrogen protection is cooled to -5 DEG C, and the grignard reagent prepared is transferred to dropping funel In, it is slowly added dropwise, system temperature is kept to be no more than 10 DEG C, 30min is stirred after being added dropwise and is then slowly increased to room temperature, is examined after 5h Raw material end of reaction is surveyed, is added dropwise saturated aqueous ammonium chloride into reaction solution, stirring 5min adds methylene chloride extraction, takes organic phase Decompression is spin-dried for, and residue is chromatographed to obtain intermediate 2-73-1 (yield 40%) by column.
The synthesis of intermediate 2-73-2: the 6- methoxybenzothiophene of 0.1mol being added in 170ml methylene chloride and is stirred, The Br of 0.1mol is added dropwise2Solution is warming up to reflux after completion of dropwise addition.Raw material end of reaction is detected after 5h, is added dropwise into reaction solution Water 500ml has a large amount of solids to be precipitated, and stirring half an hour is obtained by filtration residue and chromatographs to obtain intermediate 2-73-2 (yield by column 62%).
The synthesis of intermediate 2-73-3: preparing grignard reagent, and synthetic method obtains centre with the synthesis of intermediate 2-73-1 Body 2-73-3 (yield 40%).
The synthesis of intermediate 2-73-4: preparing grignard reagent, and synthetic method obtains centre with the synthesis of intermediate 2-73-1 Body 2-73-4 (yield 40%).
The synthesis of intermediate 2-73-5: the intermediate 2-73-4 of 0.01mol is dissolved in 50ml methylene chloride, 0.01mol Boron tribromide, react 2h at room temperature, take organic phase decompression be spin-dried for, residue is chromatographed to obtain intermediate 2-73-5 by column (yield 70%).
The synthesis of intermediate 2-73-6: the intermediate 2-73-5 of 0.007mol is dissolved in 30ml methylene chloride, is added dropwise three Fluorine methanesulfonic acid acid anhydride, reacts 5h at room temperature, takes organic phase decompression to be spin-dried for, residue is chromatographed to obtain intermediate 2-73-6 by column (yield 90%).
The synthesis of compound 2-73: the intermediate 2-73-6 of 0.0063mol is dissolved in 30ml toluene solvant, nitrogen protection Under sequentially add the carbazole, 0.016mol sodium tert-butoxide, 0.000063mol tri-tert-butylphosphine, 0.000063mol of 0.0063mol Tris(dibenzylideneacetone) dipalladium, stirring are warming up to back flow reaction, detect raw material end of reaction after 4h, reaction solution is depressurized and is revolved It is dry, it chromatographs to obtain compound 2-73 (yield 80%) by column.
Calculated value C36H21N3SSi:555.72 ± 1.δ=7.23~7.33 1H-NMR (400MHz, CDCl3) (ppm) (7H, m), 7.49~7.51 (3H, m), 7.63~7.64 (1H, m), 7.79~7.80 (1H, m), 7.94~7.95 (3H, m), 8.02~8.12 (3H, m), 8.55~8.63 (3H, m).
Embodiment 1: organic luminescent device is prepared
Successively there is with distilled water and methanol supersound washing tin indium oxide (ITO) electrode (the first electricity of about 1500 angstroms of thickness Pole, anode) glass substrate after, washed glass substrate is dry, move on to plasma cleaning system, then use oxygen Plasma cleaning about 5 minutes.Then the glass substrate is loaded into vacuum deposition device.
To there is in the ITO electrode of HAT-CN vacuum deposition to the glass substrate with formation the HIL of about 100 angstroms of thickness； The HTL with about 400 angstroms of thickness will be formed in TAPC vacuum deposition to hole injection layer.
Compound 1-1 is deposited on the hole transporting zone to form the EML with about 300 angstroms of thickness.
Then, TPBi vacuum deposition is had on the EML with formation to the ETL of about 300 angstroms of thickness.Then, LiF is sunk Product forms the EIL with about 5 angstroms of thickness on ETL, and Al is deposited on the EIL up to about 1000 angstroms of thickness to be formed Second electrode (cathode) thus completes the manufacture of organic luminescent device.
Remaining embodiment
The organic luminescent device of remaining embodiment is prepared using method similar to Example 1, the difference is that using table Compound 1-1 in 1 compound represented alternative embodiment 1.
Comparative example 1
Organic luminescent device is prepared using with similar method in embodiment 1, the difference is that replacing using compound BD-1 Change the compound 1-1 in embodiment 1.
Comparative example 2
Organic luminescent device is prepared using with similar method in embodiment 1, the difference is that replacing using compound BD-2 Change the compound 1-1 in embodiment 1.
Evaluation: the evaluating characteristics of organic luminescent device
It is measured using current-voltage source meter (Keithley 2400) and Minolta CS-1000A spectroradiometer real Apply driving voltage, emission effciency and the service life of the organic luminescent device in example and comparative example.As a result it is shown in the following table 1.
(1) measurement relative to the current density change of voltage change
By using current-voltage source meter (Keithley 2400) make voltage from while increasing to about 10V for 0 volt (V) Measurement flows through the current value of each of the organic luminescent device, then by its divided by the area of corresponding luminescent device with Obtain current density.
(2) measurement relative to the brightness change of voltage change
By using Minolta CS-1000A spectroradiometer make voltage from survey while about 0V increases to about 10V Measure the brightness of the organic luminescent device.
(3) measurement of emission effciency
Based on organic light emission described in current density, voltage and the brightness calculation obtained as measurement (1) and (2) described above Device is in 20 milliamps per square centimeter of (mA/cm2) certain current density under current efficiency.
(4) measurement in service life
Keep 5000cd/m2Brightness (cd/m2), and measure the time that current efficiency (cd/A) is decreased to 50%.
Table 1
Luminescent layer Driving voltage (V) Efficiency (cd/A) Half-life (hrs)
Embodiment 1 1-1 3.65 4.64 470
Embodiment 2 1-6 3.62 4.69 471
Embodiment 3 1-17 3.38 4.99 491
Embodiment 4 1-22 3.47 4.88 481
Embodiment 5 1-31 3.32 5.03 497
Embodiment 6 1-39 3.59 4.71 472
Embodiment 7 1-42 3.58 4.78 475
Embodiment 8 1-46 3.39 4.95 487
Embodiment 9 1-47 3.45 4.91 482
Embodiment 10 1-50 3.51 4.83 478
Embodiment 11 1-56 3.54 4.79 476
Embodiment 12 1-61 3.63 4.74 473
Embodiment 13 1-65 3.48 4.87 479
Embodiment 14 1-2 3.42 4.93 484
Embodiment 15 1-85 3.52 4.81 477
Embodiment 16 1-101 3.66 4.65 466
Embodiment 17 2-26 3.65 4.75 473
Embodiment 18 2-53 3.47 4.89 479
Embodiment 19 2-73 3.72 4.57 462
Embodiment 20 2-85 3.53 4.73 482
Comparative example 1 BD-1 4.32 3.46 337
Comparative example 2 BD-2 4.58 3.24 328
The experimental result shown in the table 1, which can be seen that the organic electroluminescence device that the compound of the present invention is formed, to be had Low driving voltage and obviously compared with the prior art higher service life and luminous efficiency.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (10)

1. a kind of organic electroluminescent compounds, which has structure shown in formula (I),
In the structure shown in formula (I),
X is O or S；
Z is Si or C；
Y1、Y2、Y3、Y4、Y5、Y6、Y7And Y8In two atoms be N atom, remaining six atoms are C atom, and two N originals Son is non-conterminous；
R1And R2It is each independently selected from H, miscellaneous three cyclic group of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted nitrogenous virtue Miscellaneous four cyclic group, miscellaneous five cyclic group of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted hexichol amido and substituted phenyl At least one of；
R1And R2In the substituent group that is optionally present be each independently selected from C1-4Alkyl, phenyl, xenyl, dibenzofuran group, At least one of the carbazyl that dibenzothiophene, fluorenyl, carbazyl, hexichol amido and phenyl replace；
Preferably,
The nitrogenous miscellaneous tricyclic of virtue in substituted or unsubstituted nitrogenous miscellaneous three cyclic group of virtue is shown in formula (a1) or formula (a2) Tricyclic, and arbitrarily C-C can be passed through at the parent nucleus in the position of key connection and formula (I) in tricyclic shown in formula (a1) and formula (a2) Key or C-N key connection；
Wherein, the Y in formula (a2) is O, S, C or N atom；
And C atom in tricyclic shown in formula (a1) and formula (a2) and/or N atom are optionally by being selected from C1-4Alkyl, phenyl, connection In the carbazyl that phenyl, dibenzofuran group, dibenzothiophene, fluorenyl, carbazyl, hexichol amido and phenyl replace at least A kind of group substitution；
Preferably,
The nitrogenous miscellaneous Fourth Ring of virtue in substituted or unsubstituted nitrogenous miscellaneous four cyclic group of virtue is selected from formula (b1) and/or formula (b2) institute The Fourth Ring shown,
And the C atom in Fourth Ring shown in formula (b1) and formula (b2) is optionally by being selected from C1-4Alkyl, in phenyl and xenyl extremely A kind of few group replaces；
Preferably,
The nitrogenous miscellaneous five rings of virtue in substituted or unsubstituted nitrogenous miscellaneous five cyclic group of virtue is selected from formula (c1) to shown in formula (c12) Five rings,
And X of the formula (c1) into formula (c12)1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11And X12Be each independently selected from O, S, C and N atom；
And C atom in five rings shown in formula (c1) to formula (c12) and/or N atom are optionally by being selected from C1-4Alkyl and phenyl At least one of group replace；
2. compound according to claim 1, wherein structure shown in the formula (I) is following formula (I1) to formula (I5) Shown at least one of structure:
And in the structure shown in formula (I1) to formula (I5), R1、R2, the definition of X and Z it is corresponding with the definition in claim 1 It is identical.
3. compound according to claim 1, wherein structure shown in the formula (I) is formula (I1) compound represented:
And in the structure shown in formula (I1), R1、R2, the definition of X and Z it is corresponding identical as the definition in claim 1；
Preferably,
Structure shown in the formula (I) is any one in compound shown below:
4. compound according to claim 1, wherein structure shown in the formula (I) is formula (I2) compound represented:
And in the structure shown in formula (I2), R1、R2, the definition of X and Z it is corresponding identical as the definition in claim 1；It is preferred that Ground,
Structure shown in the formula (I) is any one in compound shown below:
5. compound according to claim 1, wherein structure shown in the formula (I) is formula (I3) compound represented:
And in the structure shown in formula (I3), R1、R2, the definition of X and Z it is corresponding identical as the definition in claim 1；It is preferred that Ground,
Structure shown in the formula (I) is any one in compound shown below:
6. compound according to claim 1, wherein structure shown in the formula (I) is formula (I4) compound represented:
And in the structure shown in formula (I4), R1、R2, the definition of X and Z it is corresponding identical as the definition in claim 1；It is preferred that Ground,
Structure shown in the formula (I) is any one in compound shown below:
7. compound according to claim 1, wherein structure shown in the formula (I) is formula (I5) compound represented:
And in the structure shown in formula (I5), R1、R2, the definition of X and Z it is corresponding identical as the definition in claim 1；It is preferred that Ground,
Structure shown in the formula (I) is any one in compound shown below:
8. compound according to claim 1, wherein structure shown in the formula (I) is in compound in detail below Any one:
；
Preferably,
Structure shown in the formula (I) is any one in compound in detail below:
9. organic electroluminescent compounds answering in organic electroluminescence device described in any one of claim 1-8 With.
10. it is a kind of containing one or both of organic electroluminescent compounds described in any one of claim 1-8 with On compound organic electroluminescence device；Preferably,
The organic electroluminescent compounds are present in electron transfer layer, luminescent layer and the hole resistance of the organic electroluminescence device In at least one layer in barrier；Preferably,
The organic electroluminescent compounds are present in the luminescent layer of the organic electroluminescence device；Preferably,
The organic electroluminescent compounds are as the luminescent layer；Preferably,
The organic electroluminescence device includes the substrate being cascading, anode, hole injection layer, hole transmission layer, appoints Electronic barrier layer, luminescent layer, optional hole blocking layer, electron transfer layer, electron injecting layer and the cathode of choosing.
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