CN109956964A - Bipolarity organic electroluminescent compounds and its application and organic electroluminescence device - Google Patents

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

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CN109956964A
CN109956964A CN201811602621.1A CN201811602621A CN109956964A CN 109956964 A CN109956964 A CN 109956964A CN 201811602621 A CN201811602621 A CN 201811602621A CN 109956964 A CN109956964 A CN 109956964A
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layer
carbazyl
organic electroluminescent
electroluminescent compounds
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CN109956964B (en
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吕瑶
贾学艺
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 bipolarity organic electroluminescent compounds and its application and organic electroluminescence device, which has structure shown in formula (I), wherein in formula (I), X1For Si or C；X2For S or O.Aforementioned bipolarity organic electroluminescent compounds provided by the invention can significantly improve luminous efficiency when being used as in organic electroluminescence device and extend the service life of material.

Description

Bipolarity 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 bipolarity organic electroluminescent compounds, Application of the bipolarity organic electroluminescent compounds in organic electroluminescence device a kind of contains the bipolarity organic electroluminescence The organic electroluminescence device of the compound of one or more of luminophor.
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, curved surface, thin The features such as type.
The performance of OLED is not only influenced by illuminator, in particular, forming each layer of the material of OLED all to OLED Performance there is very important influence, such as base material, hole barrier materials, electron transport material, hole mobile material With 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, cause that the preferable organic electroluminescence device of performance can not be obtained.
Summary of the invention
The purpose of the invention is to overcome the luminous efficiency of organic electroluminescence device of the existing technology not high with And the defect that service life is not grown, a kind of new bipolarity organic electroluminescent compounds, bipolarity organic electroluminescence hair are provided Optical compounds can significantly reduce driving voltage, improve luminous efficiency and extension when being used as in electroluminescent organic material The service life of material.
To achieve the goals above, the first aspect of the present invention provides a kind of bipolarity organic electroluminescent compounds, should Compound has structure shown in formula (I),
Wherein, in formula (I),
X1For Si or C；
X2For S or O；
R1And R2It is each independently selected from H, the miscellaneous tricyclic of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted nitrogenous virtue Miscellaneous five rings, and R1And R2It is not simultaneously H；
R1And R2On substituent group be each independently selected from phenyl, xenyl, dibenzofuran group, dibenzothiophene, fluorenes At least one of the carbazyl that base, pyridyl group, carbazyl and phenyl replace.
The second aspect of the present invention provides bipolarity organic electroluminescent compounds described in first aspect in organic electroluminescence Application in luminescent device.
The third aspect of the present invention provides a kind of containing in bipolarity organic electroluminescent compounds described in first aspect One or more kinds of compounds organic electroluminescence device.
Aforementioned bipolarity organic electroluminescent compounds provided by the invention can regulate and control electroluminescent organic material HOMO energy level and lumo energy can be improved the utilization rate of the exciton of organic electroluminescence device luminescent layer, shine to improve Efficiency.
The present inventor has found that aforementioned bipolar organic compound provided by the invention is as organic under study for action When in electroluminescent device have preferable thermodynamic stability, good film forming, can significantly reduce driving voltage and Extend the service life of material.
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 bipolarity organic electroluminescent compounds, the compound With structure shown in formula (I),
Wherein, in formula (I),
X1For Si or C；
X2For S or O；
R1And R2It is each independently selected from H, the miscellaneous tricyclic of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted nitrogenous virtue Miscellaneous five rings, and R1And R2It is not simultaneously H；
R1And R2On substituent group be each independently selected from phenyl, xenyl, dibenzofuran group, dibenzothiophene, fluorenes At least one of the carbazyl that base, pyridyl group, carbazyl and phenyl replace.
According to a kind of preferred embodiment, in formula (I),
The nitrogenous miscellaneous tricyclic of virtue in the substituted or unsubstituted nitrogenous miscellaneous tricyclic of virtue is carbazyl shown in formula 1, and formula 1 Shown at least one of the carbazyl of carbazyl optionally by replacing selected from phenyl, xenyl, pyridyl group, carbazyl and phenyl Group replaces；
In aforementioned preferred embodiment, there is no special for the number for the substituent group that the nitrogenous miscellaneous tricyclic of virtue may contain Other restriction, such as can be 1-3；And do not have to the position of substitution for the substituent group that may contain in the nitrogenous miscellaneous tricyclic of virtue yet Special to limit, can be arbitrary being capable of substituted position.
According to another preferred embodiment, in the present invention, in formula (I),
The nitrogenous miscellaneous five rings of virtue in the substituted or unsubstituted nitrogenous miscellaneous five rings of virtue is selected from group shown in formula 2- formula 7, And group shown in formula 2- formula 7 is optionally by the carbazyl that phenyl, xenyl, pyridyl group, carbazyl and phenyl replace At least one group replaces,
In formula 2- formula 7, X3、X4、X5、X6、X7And X8It is each independently selected from -O— With-S-；And R therein11For phenyl or xenyl；R12And R13It is each independently C1-10Alkyl or phenyl；
Preferably, any one of the compound of structure shown in formula (I) in following structural formula:
Wherein, in formula 1-1, formula 1-2, formula 1-3 and formula 1-4,
R1And R2It is each independently selected from H, the miscellaneous tricyclic of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted nitrogenous virtue Miscellaneous five rings, and R1And R2It is not simultaneously H；
R1And R2On substituent group be each independently selected from phenyl, xenyl, dibenzofuran group, dibenzothiophene, fluorenes At least one of the carbazyl that base, pyridyl group, carbazyl and phenyl replace.
According to a kind of particularly preferred specific embodiment, in the present invention, the compound of structure shown in formula (I) is selected from Any one in claim 5 in cited particular compound.
According to another preferred specific embodiment, in order to further increase the luminous efficiency of organic luminescent device, In the present invention, any one in the compound of structure shown in formula (I) particular compound cited in claim 6 Kind.
There is no particular limitation to the specific method for preparing aforementioned bipolarity organic electroluminescent compounds by the present invention, ability Several tools that the concrete structure formula and specific example part of the invention that field technique personnel can provide according to the present invention are enumerated The preparation method of body compound and the preparation method for obtaining whole bipolarity organic electroluminescent compounds of the invention.The present invention The preparation method of whole bipolarity organic electroluminescent compounds is not enumerated specifically herein, those skilled in the art cannot It is interpreted as limitation of the present invention.
As previously mentioned, the second aspect of the present invention provides bipolarity organic electroluminescent described in aforementioned first aspect Close application of the object in organic electroluminescence device.
As previously mentioned, the third aspect of the present invention provide it is a kind of containing bipolarity Organic Electricity described in aforementioned first aspect The organic electroluminescence device of the compound of one or more of electro luminescent compounds.
Under preferable case, the bipolarity organic electroluminescent compounds are present in the electronics of the organic electroluminescence device In at least one layer in transport layer, luminescent layer and hole blocking layer.
According to a kind of preferred embodiment, the bipolarity organic electroluminescent compounds are present in the Organic Electricity In the hole blocking layer of electroluminescence device, and as hole barrier materials.
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 Bipolarity organic electroluminescent compounds 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: compound 1-1-7
The synthesis of intermediate 1-1-7-1: will be stirred in bis- (2- bromophenyl) the sulfanes addition anhydrous THF of 200ml of 0.059mol, N2- 78 DEG C are cooled under protection, the n-BuLi 0.118mol of 2.5mol/L is added dropwise, -78 DEG C of heat preservation is added totally after 1 hour The silicon tetrachloride of 0.059mol.Raw material end of reaction is detected after being warming up to 25 DEG C of holding 5h, saturation chlorination is added dropwise into reaction solution Aqueous ammonium, stirring 5min add methylene chloride extraction, take organic phase to depressurize and are spin-dried for, residue is chromatographed to obtain intermediate by column 1-1-7-1 (yield 46%).
Calculated value C12H8Cl2SSi:283.25 ± 1.δ=7.11~7.11 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.26~7.35 (4H, m), 7.51~7.52 (2H, m).
The synthesis of intermediate 1-1-7-2: synthetic method obtains intermediate 1-1-7-2 with the synthesis of intermediate 1-1-7-1 (yield 53%).
Calculated value C22H14N2SSi:366.51 ± 1.1H-NMR (400MHz, CDCl3) δ=7.11~7.11 (ppm) (2H, m), 7.24~7.35 (6H, m), 7.51~7.52 (2H, m), 7.93~7.94 (2H, m), 8.63~8.64 (2H, m).
The synthesis of intermediate 1-1-7-3: 0.0143mol intermediate 1-1-7-2 being added in the DMF of 53ml and stirred, temperature control 0 DEG C, the 0.0286mol of NBS is added, is warming up to 50 DEG C, detects raw material end of reaction after reaction 4 hours, reaction solution adds water 100ml Solid is precipitated, product is obtained by filtration, residue is chromatographed to obtain intermediate 1-1-7-3 (yield 45%) by column.
Calculated value C22H12Br2N2SSi:524.30 ± 1.δ=7.24~7.26 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.40~7.41 (2H, m), 7.51~7.52 (2H, m), 7.81~7.82 (2H, m), 7.94~7.95 (2H, m), 8.63~8.64 (2H, m).
The synthesis of compound 1-1-7: 6.4mmol intermediate 1-1-7-3 is dissolved in 20ml toluene solvant, is stirred under logical nitrogen Mix, sequentially add 7,7- dimethyl -5,7- dihydro indeno [2,1-b] carbazole of 0.0128mol, 0.03mol sodium tert-butoxide, Tri- dibenzalacetone of 0.06mmol, two palladium, 0.06mmol) tri-tert-butylphosphine, it is warming up to reflux, detects, has reacted after reacting 8h Finish, stop reaction, reaction solution decompression is spin-dried for, and obtained residue is recrystallized to give compound 1-1-7 (yield with dimethylbenzene 61%).
Calculated value C64H44N4SSi:929.21 ± 1.δ=1.72~1.72 1H-NMR (400MHz, CDCl3) (ppm) (12H, s), 7.24~7.29 (6H, m), 7.44~7.52 (10H, m), 7.61~7.69 (6H, m), 7.93~7.94 (2H, m), 8.09~8.12 (4H, m), 8.39~8.39 (2H, s), 8.62~8.63 (2H, m).
Preparation example 2: compound 1-1-12
The synthesis of intermediate 1-1-12-1: 0.0076mol intermediate 1-1-7-2 being added in the DMF of 30ml and stirred, temperature control 0 DEG C, the 0.0076mol of NBS is added, is warming up to 50 DEG C, detects raw material end of reaction after reaction 4 hours, reaction solution adds water 150ml Solid is precipitated, product is obtained by filtration, residue is chromatographed to obtain intermediate 1-1-12-1 (yield 48%) by column.
Calculated value C22H12Br2N2Ssi:445.41 ± 1.δ=7.11~7.13 1H-NMR (400MHz, CDCl3) (ppm) (1H, m), 7.24~7.51 (5H, m), 7.51~7.52 (2H, m), 7.81~7.82 (1H, m), 7.94~7.95 (2H, m), 8.63~8.64 (2H, m).
The synthesis of compound 1-1-12: synthetic method obtains compound 1-1-12 (yield with the synthesis of compound 1-1-7 63%).
Preparation example 3: compound 1-2-7
The synthesis of intermediate 1-2-7-1: synthetic method obtains intermediate 1-2-7-1 with the synthesis of intermediate 1-1-7-1 (yield 53%).
Calculated value C12H8Cl2Osi:267.18 ± 1.δ=7.09~7.10 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.24~7.25 (2H, m), 7.42~7.51 (4H, m).
The synthesis of intermediate 1-2-7-2: synthetic method obtains intermediate 1-2-7-2 with the synthesis of intermediate 1-1-7-1 (yield 49%).
Calculated value C22H14N2OSi:350.44 ± 1.δ=7.09~7.09 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.24~7.26 (4H, m), 7.42~7.51 (4H, m), 7.93~7.94 (2H, m), 8.63~8.64 (2H, m).
The synthesis of intermediate 1-2-7-3: synthetic method obtains intermediate 1-2-7-3 with the synthesis of intermediate 1-1-7-3 (yield 52%).
Calculated value C22H12Br2N2OSi:508.24 ± 1.δ=7.13~7.14 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.24~7.26 (2H, m), 7.66~7.67 (4H, m), 7.93~7.94 (2H, m), 8.63~8.64 (2H, m).
The synthesis of compound 1-2-7: synthetic method obtains compound 1-2-7 (yield with the synthesis of intermediate 1-1-7 55%).
Calculated value C58H36N4OSi:833.02 ± 1.δ=7.24~7.29 1H-NMR (400MHz, CDCl3) (ppm) (4H, m), 7.41~7.52 (12H, m), 7.62~7.68 (8H, m), 7.93~7.94 (2H, m), 8.10~8.12 (4H, m), 8.49~8.63 (4H, m).
Preparation example 4: compound 1-2-16
The synthesis of intermediate 1-2-16-1: 0.0096mol intermediate 1-2-2-2 being added in the DMF of 30ml and stirred, temperature control 0 DEG C, the 0.0091mol of NBS is added, is warming up to 50 DEG C, detects raw material end of reaction after reaction 4 hours, reaction solution adds water 150ml Solid is precipitated, product is obtained by filtration, residue is chromatographed to obtain intermediate 1-2-16-1 (yield 48%) by column.
Calculated value C22H13BrN2OSi:429.34 ± 1.δ=7.09~7.13 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7., 24~7.26 (3H, m), 7.42~7.51 (2H, m), 7.94~7.96 (2H, m), 8.63~8.65 (2H, m).
The synthesis of compound 1-2-16: synthetic method obtains compound 1-2-16 (yield with the synthesis of compound 1-1-7 58%).
Calculated value C43H29N3O:631.80 ± 1.δ=1.72~1.72 1H-NMR (400MHz, CDCl3) (ppm) (6H, S), 7.09~7.11 (1H, m), 7., 24~7.33 (8H, m), 7.42~7.51 (3H, m), 7.61~7.69 (4H, m), 7.94 ~7.96 (3H, m), 8.09~8.11 (1H, m), 8.55~8.57 (1H, m), 8.63~8.65 (2H, m).
Preparation example 5: compound 1-3-1
The synthesis of intermediate 1-3-1-1: the chloro- 2- phenyl sulfonyl benzene (0.05mol) of 1- is added under nitrogen atmosphere in three In mouth flask, 110ml anhydrous tetrahydro furan is added.The positive fourth of 2.4M is added dropwise in constant pressure funnel after stirring 10min at -78 DEG C Base lithium (0.055mol).1h is reacted, the anhydrous tetrahydro furan being slowly added dropwise dissolved with 4,5- diaza fluorenes -9- ketone (0.05mol) is molten Liquid (200mL) after reacting 1h, warms naturally to 25 DEG C overnight, 25mL water quenching reaction is added dropwise after completion of the reaction.Solvent is removed, Methylene chloride and water extract, and take organic phase, are evaporated methylene chloride and obtain yellow solid 17.52g, without any processing to be directly entered It reacts in next step.
Calculated value C23H14N2S:350.44 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H,m), 7.03~7.07 (4H,m), 7.33~7.33 (2H,m), 7.48~7.48 (2H,m), 7.65~7.65 (2H,m), 8.51 ~8.51 (2H, m).
The synthesis of intermediate 1-3-1-2: 0.05mol intermediate 1-3-1-1 is dissolved in the N,N-dimethylformamide of 180ml In, 50 DEG C are warming up to, the NBS of the 0.1mol dissolved with the n,N-Dimethylformamide of 150ml is added dropwise, is added dropwise and is warming up to 100 DEG C of stirring 2h detect raw material end of reaction, reaction solution are cooled to room temperature, water 300ml is added dropwise, stirring 20min filtering, drying Obtain intermediate 1-3-1-2 (yield 50%).
Calculated value C23H12Br2N2S:508.23 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.18~7.18 (4H, m), 7.48~7.52 (4H, s), 8.51~8.51 (2H, m).
The synthesis of compound 1-3-1: 0.025mol intermediate 1-3-1-2 is dissolved in 130ml toluene solvant, is led under nitrogen Stirring, then sequentially add 0.05mol carbazole, 0.075mol sodium tert-butoxide, 0.0025mol three dibenzalacetones, two palladium, 0.0025mol tri-tert-butylphosphine is warming up to back flow reaction, detects raw material end of reaction after 6h, reaction solution decompression is spin-dried for, is passed through Column chromatographs to obtain compound 1-3-1 (yield 55%).
Calculated value C47H28N4S:680.82 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.23~7.36 (12H, m), 7.48~7.50 (4H, m), 7.63~7.63 (2H, m), 7.94~7.94 (2H, m), 8.12 ~8.12 (2H, m), 8.51~8.55 (4H, m).
Preparation example 6: compound 1-3-2
The synthesis of compound 1-3-2: synthetic method obtains compound 1-3-2 (yield 58%) with compound 1-3-1.
Calculated value C59H36N4S:833.01 ± 1.δ=6.81~6.82 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.23~7.52 (22H, m) 7.62~7.64 (2H, d), 7.79~7.81 (2H, m), 7.94~7.96 (2H, m), 8.18~ 8.20 (2H, d), 8.51~8.55 (4H, m).
Preparation example 7: compound 1-3-12
The synthesis of intermediate 1-3-12-1: synthetic method obtains intermediate 1-3-12-1 (yield with intermediate 1-3-1-2 59%).
Calculated value C23H13BrN2S:429.33 ± 1.δ=6.81~6.83 1H-NMR (400MHz, CDCl3) (ppm) (2H, m), 7.03~7.07 (2H, m), 7.18~7.20 (2H, m), 7.33~7.33 (1H, m), 7.48~7.52 (3H, m), 7.65~7.65 (1H, m), 8.51~8.53 (2H, m).
The synthesis of compound 1-3-12: synthetic method obtains compound 1-3-12 (yield 58%) with compound 1-3-1.
Calculated value C47H28N4S:680.82 ± 1.δ=6.81~6.81 1H-NMR (400MHz, CDCl3) (ppm) (2H, M), 7.03~7.07 (2H, m), 7.25~7.65 (19H, m), 7.94 (1H, m), 8.12 (1H, m), 8.51~8.55 (3H, m)
Preparation example 8: compound 1-4-1
The synthesis of intermediate 1-4-1-1: under nitrogen atmosphere, three-necked flask is added in the 2- chlorodiphenyl ether of 0.0977mol In, 200ml anhydrous tetrahydro furan is added.2.4M n-BuLi is added dropwise in constant pressure funnel after stirring 10min at -78 DEG C (0.1192mol).1h is reacted, the anhydrous tetrahydrofuran solution dissolved with 4,5- diaza fluorenes -9- ketone (0.0294mol) is slowly added dropwise (50mL) after reacting 1h, warms naturally to 25 DEG C overnight, 5mL water quenching reaction is added dropwise after completion of the reaction.Remove solvent, dichloro Methane and water extract, and take organic phase, are evaporated methylene chloride and obtain yellow solid 22.4g, it is without any processing be directly entered it is next Step reaction.
Calculated value C23H14N2O:334.37 ± 1.δ=6.81 (2H, m) 1H-NMR (400MHz, CDCl3) (ppm), 7.05 (2H, m), 7.19~7.22 (6H, m), 7.48 (2H, m), 8.51 (2H, m).
The synthesis of intermediate 1-4-1-2: 0.0670mol intermediate 1-4-1-1 is dissolved in the N of 220ml, N- dimethyl formyl In amine, 50 DEG C are warming up to, the NBS of the 0.1340mol dissolved with the n,N-Dimethylformamide of 150ml is added dropwise, liter is added dropwise Water 900ml is added dropwise in temperature to 100 DEG C of stirring 2h, detection raw material end of reaction after reaction solution is down to 25 DEG C, stirring 20min is filtered, Drying obtains intermediate 1-4-1-2 (yield 58%).
Calculated value C23H12Br2N2O:492.16 ± 1.δ=6.81 (2H, m) 1H-NMR (400MHz, CDCl3) (ppm), 7.35 (2H, m), 7.48 (2H, m), 7.63 (2H, m), 8.51 (2H, m).
The synthesis of compound 1-4-1: the intermediate 1-4-1-2 of 0.0389mol is dissolved in 200ml toluene, is led under nitrogen Stirring, sequentially adds the carbazole of 0.0778mol, 0.0973mol sodium tert-butoxide, 0.10g tris(dibenzylideneacetone) dipalladium, 0.26ml tri-tert-butylphosphine is warming up to back flow reaction, and HPLC detects raw material fundamental reaction and finishes after 4h, and reaction solution is depressurized and is revolved It is dry, residue is chromatographed to obtain compound 1-4-1 (yield: 60%) by column.
Calculated value C47H28N4O:664.75 ± 1.δ=6.81 (2H, m) 1H-NMR (400MHz, CDCl3) (ppm), 7.02 (2H, m), 7.25~7.50 (14H, m), 7.63 (2H, m), 7.94 (2H, m), 8.12 (2H, m), 8.51~8.55 (4H, 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.
By DMIC-TRZ and Ir (ppy)3It is that 97:3 is co-deposited on the hole transporting zone with vacuum deposition speed ratio To form the EML with about 300 angstroms of thickness.
The HBL with about 50 angstroms of thickness will be formed in compound 1-1-1 vacuum deposition to luminescent layer.
Then, compound L G201 vacuum deposition is had on the EML with formation to the ETL of about 250 angstroms of thickness.Then, LiF is deposited on to form the EIL with about 5 angstroms of thickness on ETL, and Al is deposited on the EIL up to about 1000 angstroms of thickness Degree thus completes the manufacture of organic luminescent device to form second electrode (cathode).
Remaining embodiment
The organic luminescent device of remaining embodiment is prepared using method similar to Example 1, the difference is that using table Compound 1-1-1 in 1 compound represented alternative embodiment 1.
Comparative example 1
Organic luminescent device is prepared using with similar method in embodiment 1, is implemented the difference is that being replaced using TPBi Compound 1-1-1 in example 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 10000cd/m2Brightness (cd/m2), and measure the time that current efficiency (cd/A) is decreased to 80%.
Table 1
The organic electroluminescence device formed by novel compound of present invention has low driving voltage and obvious more existing Technology higher service life, current efficiency and brightness.
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 bipolarity organic electroluminescent compounds, which has structure shown in formula (I),
Wherein, in formula (I),
X1For Si or C；
X2For S or O；
R1And R2It is each independently selected from H, the miscellaneous tricyclic of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted nitrogenous virtue miscellaneous five Ring, and R1And R2It is not simultaneously H；
R1And R2On substituent group be each independently selected from phenyl, xenyl, dibenzofuran group, dibenzothiophene, fluorenyl, At least one of the carbazyl that pyridyl group, carbazyl and phenyl replace.
2. bipolarity organic electroluminescent compounds according to claim 1, wherein in formula (I),
The nitrogenous miscellaneous tricyclic of virtue in the substituted or unsubstituted nitrogenous miscellaneous tricyclic of virtue is carbazyl shown in formula 1, and shown in formula 1 Carbazyl optionally by least one of the carbazyl that replaces selected from phenyl, xenyl, pyridyl group, carbazyl and phenyl group Replace；
3. bipolarity organic electroluminescent compounds according to claim 1 or 2, wherein in formula (I),
The nitrogenous miscellaneous five rings of virtue in the substituted or unsubstituted nitrogenous miscellaneous five rings of virtue is selected from group shown in formula 2- formula 7, and formula Group shown in 2- formula 7 optionally by the carbazyl that phenyl, xenyl, pyridyl group, carbazyl and phenyl replace at least A kind of group substitution,
In formula 2- formula 7, X3、X4、X5、X6、X7And X8It is each independently selected from - O- and-S-； And R therein11For phenyl or xenyl；R12And R13It is each independently C1-10Alkyl or phenyl；
4. bipolarity organic electroluminescent compounds according to claim 1, wherein the compound of structure shown in formula (I) Any one in following structural formula:
Wherein, in formula 1-1, formula 1-2, formula 1-3 and formula 1-4,
R1And R2It is each independently selected from H, the miscellaneous tricyclic of substituted or unsubstituted nitrogenous virtue, substituted or unsubstituted nitrogenous virtue miscellaneous five Ring, and R1And R2It is not simultaneously H；
R1And R2On substituent group be each independently selected from phenyl, xenyl, dibenzofuran group, dibenzothiophene, fluorenyl, At least one of the carbazyl that pyridyl group, carbazyl and phenyl replace.
5. bipolarity organic electroluminescent compounds according to claim 1, wherein the chemical combination of structure shown in formula (I) Any one of object in following compound:
6. bipolarity organic electroluminescent compounds according to claim 5, wherein the chemical combination of structure shown in formula (I) Any one of object in following compound:
7. bipolarity organic electroluminescent compounds described in any one of claim 1-6 are in organic electroluminescence device Application.
8. a kind of contain one of bipolarity organic electroluminescent compounds described in any one of claim 1-6 or two Kind or more compound organic electroluminescence device；Preferably,
The bipolarity organic electroluminescent compounds be present in the electron transfer layer of the organic electroluminescence device, luminescent layer and In at least one layer in hole blocking layer.
9. organic electroluminescence device according to claim 8, wherein the bipolarity organic electroluminescent compounds are deposited It is in the hole blocking layer of the organic electroluminescence device, and as hole barrier materials.
10. organic electroluminescence device according to claim 8 or claim 9, wherein the organic electroluminescence device include according to The secondary substrate being stacked, anode, hole injection layer, hole transmission layer, optional electronic barrier layer, luminescent layer, optional sky Cave barrier layer, electron transfer layer, electron injecting layer and cathode.
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