CN107089990A - A kind of organic compound as core using fluorenes and its application on organic electroluminescence device - Google Patents

A kind of organic compound as core using fluorenes and its application on organic electroluminescence device Download PDF

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CN107089990A
CN107089990A CN201710422478.7A CN201710422478A CN107089990A CN 107089990 A CN107089990 A CN 107089990A CN 201710422478 A CN201710422478 A CN 201710422478A CN 107089990 A CN107089990 A CN 107089990A
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compound
formula
organic compound
fluorenes
organic
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CN107089990B (en
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唐丹丹
李崇
张小庆
张兆超
金伟新
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

The present invention relates to a kind of organic compound as core using fluorenes and its application in OLED, the structure of the compound is that fluorenes is connected by carbon-carbon bond with dibenzo five-membered ring and ring structure, carbon-carbon bond connection had both improved materials chemistry stability, and to turn avoid the active position of branched group exposed, and whole molecule is a larger rigid structure, with high triplet (T1)；And steric hindrance is big, it is difficult to rotate, solid space structure is more stable, therefore compound has higher glass transition temperature and molecule heat endurance；In addition, HOMO the and LUMO distributing positions of the compounds of this invention are separated from each other, suitable HOMO and lumo energy are made it have；Therefore, the compounds of this invention is applied to after OLED, can effective boost device luminous efficiency and service life.

Description

A kind of organic compound using fluorenes as core and its on organic electroluminescence device Using
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of organic compound using fluorenes as core and its having Application in organic electroluminescence devices.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can for system New display product is made, can be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is quite varied.OLED luminescent devices are just as the structure of sandwich, including electrode material film layer and are clipped in different electricity Organic functional material between the film layer of pole, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED hairs together Optical device.OLED luminescent devices are as current device, when applying voltage to its two end electrodes, and pass through electric field action organic layer work( Can be in film layer positive and negative charge when, positive and negative charge is further combined in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are in smart mobile phone, and the field such as tablet personal computer is applied, further will also be to electricity Depending on etc. the extension of large scale application field, still, compare, the luminous efficiency of OLED and use with actual products application requirement The performances such as life-span also need to further lifting.Proposing high performance research to OLED luminescent devices at present includes：Reduce the drive of device Dynamic voltage, the luminous efficiency for improving device, the service life for improving device etc..In order to realize that the continuous of performance of OLED carries Rise, not only need the innovation from OLED structure and manufacture craft, with greater need for the constantly research and wound of oled light sulfate ferroelectric functional material Newly, the OLED functional materials of higher performance are formulated out.
Oled light sulfate ferroelectric functional material applied to OLED can be divided into two major classes from purposes, and respectively electric charge injects Transmission material and luminescent material.Further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking Luminescent material, can also be divided into main body luminescent material and doping material by material, hole injection transmission material and hole barrier materials Material.
In order to make high performance OLED luminescent devices, it is desirable to which various organic functional materials possess good photoelectric properties, For example, as charge transport materials, it is desirable to good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer has good bipolarity, appropriate HOMO/LUMO energy ranks etc..
Constituting the oled light sulfate ferroelectric functional material film layer of OLED at least includes what is applied in more than two layers structure, industry OLED structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electric transmission A variety of film layers such as layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED at least includes hole and injected Material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and various The characteristics of property.In addition, for the OLED collocation of different structure, used photoelectric functional material has stronger choosing Selecting property, performance of the identical material in different structure device may also be completely totally different.
Therefore, industry application requirement and the difference in functionality film layer of OLED for current OLED, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, the OLED functional materials or combination of materials that performance is higher, could realize the height of device The overall characteristic of efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, current OLED The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, is used as the organic of material enterprise development higher performance Functional material is particularly important.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide a kind of organic compound using fluorenes as core and Its application on organic electroluminescence device.The compounds of this invention contain it is fluorene structured, with higher glass transition temperature and point Sub- heat endurance, suitable HOMO and lumo energy, higher Eg is optimized by device architecture, can effectively lift OLED The life-span of photoelectric properties and OLED.Technical scheme is as follows：
The applicant provides a kind of organic compound using fluorenes as core, the structure such as formula of the organic compound (1) shown in：
In formula (1), Ar be expressed as phenyl, dibiphenylyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, One kind in thienyl, pyridine radicals, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical；
In formula (1), R is expressed as structure shown in formula (2)；
In formula (2), X is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the aryl of straight or branched alkyl substitution take One kind in the tertiary amine groups that alkylidene, the alkyl or aryl in generation replace；
In formula (2), R1It is expressed as the structure shown in formula (3)；
Wherein, a is selected fromX1、X2Independently be expressed as oxygen atom, sulphur atom, C1-10Straight chain or branch One kind in the tertiary amine groups that alkylidene, the alkylidene of aryl substitution, the alkyl or aryl of alkyl group substitution replace；
Formula (3) passes through CL1-CL2Key, CL2-CL3Key or CL3-CL4Key is connected with formula (2).
It is preferred that, the formula (2) is expressed as：
In any one.
It is preferred that, the concrete structure formula of the organic compound is：
In any one.
The applicant additionally provides the reactional equation occurred in a kind of preparation method of the organic compound, preparation process Formula is：
Specifically preparation method is：Intermediate compound I and intermediate II are weighed, is 1.5~3 with volume ratio:1 toluene ethanol mixing Solvent dissolves；Add Na2CO3The aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in anti- Answer and reacted 10~24 hours at 90~110 DEG C of temperature, cooling, filtering reacting solution, filtrate revolving cross silicagel column, obtains target Product；
The mol ratio of the intermediate compound I and intermediate II is 1:1.0~1.5；Pd(PPh3)4Mol ratio with intermediate compound I is 0.006~0.02:1, Na2CO3Mol ratio with intermediate compound I is 2.0~3.0:1.
The applicant, which additionally provides a kind of described organic compound using fluorenes as core, to be used to prepare organic electroluminescent Device.
The applicant additionally provides a kind of organic electroluminescence device, and the organic electroluminescence device includes at least one layer Functional layer contains the described organic compound using fluorenes as core.The applicant additionally provides a kind of organic electroluminescence device, Including electronic barrier layer, the electronic blocking layer material is the described organic compound using fluorenes as core.The applicant also carries A kind of organic electroluminescence device, including luminescent layer are supplied, the luminescent layer contains the described organic compound using fluorenes as core Thing.
The present invention is beneficial to be had technical effect that：
The compounds of this invention is connected using fluorenes as skeleton with dibenzo five-membered ring and ring structure with carbon-carbon bond, and carbon-carbon bond connects Connect and both improve stability of material to turn avoid the active position of branched group exposed；Firm larger except fluorenes has of such compound Property outside, dibenzo five-membered ring and ring structure are also the rigid structure of one big pi bond conjugation, and steric hindrance is big, are difficult rotation so that The stereochemical structure of the compounds of this invention material is more stablized.And the compounds of this invention triplet T1 spin density distribution Substantially on side chain, side chain has high T1 energy levels, therefore the compounds of this invention equally has high T1 energy levels；The compounds of this invention As OLED electronic barrier layer materials'use when, high T1 energy levels can effectively stop energy from luminescent layer to hole transmission layer Transmission, reduce energy loss, luminescent layer material of main part energy is sufficiently transmitted to dopant material so that lifted materials application in Luminous efficiency after device.
The structure of the organic compound of the present invention causes electronics and hole more to be balanced in the distribution of luminescent layer, appropriate Under HOMO energy levels, hole injection and transmission performance are improved；Under suitable lumo energy, the work of electronic blocking is served again With combined efficiency of the lifting exciton in luminescent layer；As OLED luminescent devices light emitting functional layer materials'use when, fluorenes collocation Side chain in the scope of the invention can effectively improve the efficiency under exciton utilization rate and high fluorescent radiation efficiency, reduction high current density Roll-off, reduce device voltage, improve current efficiency and the life-span of device.
The organic compound of the present invention is optimized when OLED is applied by device architecture, and high film layer can be kept steady It is qualitative, the photoelectric properties of OLED and the life-span of OLED can be effectively lifted, with good application effect and industry Change prospect.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED；Wherein, 1, transparent substrate layer, 2nd, ito anode layer, 3, hole injection layer, 4, hole transmission layer 5, electronic barrier layer, 6, luminescent layer, 7, hole barrier/electronics passes Defeated layer, 8, electron injecting layer, 9, negative electrode reflection electrode layer.
Embodiment
Embodiment 1：The synthesis of intermediate compound I and intermediate II
A. the synthesis of intermediate compound I：
(1) raw material U and Mg powder is weighed, is dissolved with dry tetrahydrofuran (THF)；Under an inert atmosphere, catalytic amount is added I2, it is heated to 40 DEG C of stirring to solution and is become colorless by yellow, then above-mentioned mixed solution is heated at 60~90 DEG C, stir Reaction 3-5 hours, no magnesium powder is remaining, and reaction is complete, generation grignard reagent intermediate V；The mol ratio of the raw material U and Mg is 1: 1.0~1.2；I2Mol ratio with raw material U is 0.006~0.02:1；
(2) 9-Fluorenone is weighed, is dissolved with dry THF；Under an inert atmosphere, above-mentioned grignard reagent intermediate V is added dropwise, by institute Mixed solution is obtained at 60~90 DEG C, stirring reaction 10-24 hours generates a large amount of white precipitates, is subsequently cooled to room temperature, adds Form salt is converted into alcohol by saturation NHCl4；After completion of the reaction, ether is extracted, and dries revolving, is crossed silicagel column, is obtained yellowish Solid tertiary alcohol intermediates W；The 9-Fluorenone and intermediate V mol ratio are 1:1.0~1.2；
(3) intermediate W is weighed, is dissolved with toluene；The 48%HBr aqueous solution is slowly added dropwise in mixed solution, 20~25 Stirring reaction 15-30 hours at DEG C, point liquid after reaction terminates, aqueous phase is extracted with toluene, and organic phase uses anhydrous sodium sulfate after merging Dry, suction filtration, filter cake uses ethyl acetate rinse again, filtrate and flushing liquor are rotated to solvent-free, silicagel column is crossed, obtains intermediate I.The volume of the 48%HBr aqueous solution is 20ml correspondences per 0.01mol intermediates W.
By taking intermediate M1 synthesis as an example：
(1) 250mL there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.05mol raw materials U1,0.06molMg powder, uses 60ml dry tetrahydrofurans dissolve, and add 0.0004mol simple substance I2, it is heated to 40 DEG C of stirring to solution and is become colorless by yellow, Above-mentioned mixed solution is heated at 80 DEG C, stirring reaction 4 hours, no magnesium powder is remaining, reaction is complete, in the middle of generation grignard reagent Body V1, without purification, directly carries out next step.
(2) 250mL there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.03mol9- Fluorenones, tetrahydrochysene is dried with 40ml Furans dissolves, and above-mentioned grignard reagent intermediate V1 solution is slowly added dropwise, is heated to reflux 15 hours, generates a large amount of white precipitates, so After be cooled to room temperature, add saturation NHCl4Form salt is converted into alcohol；After completion of the reaction, ether is extracted, and dries revolving, crosses silicon Glue post, obtains solid tertiary alcohol intermediates W1, the HPLC purity 99.5% of yellowish, yield 74.2%.
Elementary analysis structure (molecular formula C25H18O)：Theoretical value C, 89.79；H,5.43；O,4.78；Test value：C, 89.78；H,5.42；O,4.80.ESI-MS(m/z)(M+)：Theoretical value 334.14, measured value is 334.42.
(3) 250mL there-necked flask, adds 0.02mol intermediate W1, is dissolved with 50ml toluene, 48%HBr water is slowly added dropwise Solution (40ml), stirring reaction 24 hours at 25 DEG C, point liquid after reaction terminates, aqueous phase is extracted with toluene, after organic phase merges With anhydrous sodium sulfate drying, suction filtration, filter cake uses ethyl acetate rinse again, and filtrate and flushing liquor are rotated to solvent-free, silica gel is crossed Post, obtains intermediate M1, HPLC purity 99.4%, yield 73.5%.
Elementary analysis structure (molecular formula C25H17Br)：Theoretical value C, 75.58；H,4.31；Br,20.11；Test value：C, 75.57；H,4.33；Br,20.10.ESI-MS(m/z)(M+)：Theoretical value 396.05, measured value is 396.34.
Intermediate compound I is prepared with intermediate M1 synthetic method, synthesis is divided into three steps：By raw material U and Mg powder synthetic intermediate V；Intermediate V and 9-Fluorenone synthetic intermediate W, then by intermediate W and 48%HBr Syntheses in water intermediate compound I, concrete structure As shown in table 1.
Table 1
B. intermediate II is R-B (OH)2Synthesis：
b1:The synthesis of intermediate II -1 (X is oxygen atom):
(1) weigh raw material A to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and slowly It is added dropwise in the acetic acid solution of raw material A, 5h is stirred at room temperature, sample point plate, display raw material A is remaining, and reaction is complete；Reaction terminates Afterwards, alkali lye being added into reaction solution to neutralize, being extracted with dichloromethane, be layered, take organic phase to filter, filtrate decompression, which is rotated to nothing, to be evaporated Point, silicagel column is crossed, intermediate S1 is obtained；The mol ratio of the raw material A and bromine is 1:1~1.5；
(2) intermediate S1 and raw material B are weighed, is 1.5~3.0 with volume ratio:1 toluene alcohol mixed solvent dissolving；Again Add Na2CO3The aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by above-mentioned mixed solution at 95~100 DEG C, stirring reaction 10 ~24 hours, room temperature, filtering reacting solution are subsequently cooled to, filtrate revolving crosses silicagel column, obtains intermediate S2；The raw material B Mol ratio with intermediate S1 is 1:1.5~3.0；Pd(PPh3)4Mol ratio with raw material B is 0.006~0.02:1, Na2CO3 Mol ratio with raw material B is 2.0~3.0:1；
(3) under nitrogen protection, intermediate S2 and p-methyl benzenesulfonic acid are weighed, is dissolved with toluene, 95~100 DEG C are heated to, Reaction 10~24 hours；Sample point plate, display is remaining without intermediate S2, and reaction is complete；After reaction terminates, add into reaction system Enter saturated sodium carbonate solution to be quenched, be extracted with ethyl acetate, point liquid, vacuum rotary steam is to nothing after organic phase anhydrous sodium sulfate drying Cut, gained crude product crosses neutral silica gel post, obtains intermediate S3；The mol ratio of the intermediate S2 and p-methyl benzenesulfonic acid are 1: 1~1.5；
(4) weigh intermediate S3 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Weigh bromine to be dissolved in glacial acetic acid, and delay Slowly it is added dropwise in intermediate S3 acetic acid solution, 5h is stirred at room temperature, sample point plate, display raw material S3 is remaining, and reaction is complete；Reaction After end, into reaction solution add alkali lye neutralize, extracted with dichloromethane, be layered, take organic phase to filter, filtrate decompression rotate to Without cut, silicagel column is crossed, intermediate S4 is obtained；The mol ratio of the intermediate S4 and bromine is 1:1~1.5；
(5) under nitrogen protection, weigh intermediate S4 to be dissolved in tetrahydrofuran, be cooled to -78 DEG C, then to reaction system The tetrahydrofuran solution of middle addition 1.6mol/L n-BuLis, triisopropyl borate ester is added after reacting 3h at -78 DEG C, is reacted 2h, then rises to 0 DEG C by reaction system, adds 2mol/L hydrochloric acid solutions, stirs 3h, and reaction is complete, adds ether extraction, extraction Liquid adds anhydrous magnesium sulfate and dried, revolving, is recrystallized with alcohol solvent, obtains intermediate II -1；The intermediate S4 and positive fourth The mol ratio of base lithium is 1:1~1.5；The mol ratio of the intermediate S4 and triisopropyl borate ester are 1:1~1.5.
It is such by taking intermediate O1 synthesis as an example：
(1) 0.1mol raw material As 1 are added in 250mL there-necked flask, 50ml acetic acids are cooled to 0 DEG C with ice salt bath； 6.2ml (0.12mol) bromine for being dissolved in 20ml glacial acetic acid is added dropwise into reaction system at 0 DEG C, is warmed to room temperature, stirs 5h；Sample point plate, display raw material A 1 is remaining, and reaction is complete, after reaction terminates, and sodium carbonate liquor is added into reaction solution and is neutralized, Extracted, be layered with dichloromethane, take organic phase, dry filter, filtrate decompression rotates to without cut, crosses silicagel column, obtain centre Body S1-1, HPLC purity 99.3%, yield 66.2%.
Elementary analysis structure (molecular formula C15H13BrO2)：Theoretical value C, 59.04；H,4.29；Br,26.18；O,10.49；Survey Examination value：C,59.05；H,4.30；Br,26.17；O,10.48.ESI-MS(m/z)(M+)：Theoretical value 304.01, measured value is 304.27。
(2) 500mL there-necked flask, under nitrogen protection, adds 0.05mol raw materials B1,0.06mol intermediate S1-1, uses Mixed solvent dissolves (180ml toluene, 90ml ethanol), then adds 0.15mol Na2CO3The aqueous solution (2M), leads to nitrogen gas stirring 1 Hour, then add 0.0005mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is complete.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate S2-1, HPLC purity 99.4%, yield 68.7%.
Elementary analysis structure (molecular formula C21H18O3)：Theoretical value C, 79.22；H,5.70；O,15.08；Test value：C, 79.23；H,5.71；O,15.06.ESI-MS(m/z)(M+)：Theoretical value 318.13, measured value is 318.36.
(3) 250mL there-necked flask, under nitrogen protection, adds intermediate 0.03mol intermediates S2-1 and 0.036mol pairs Toluenesulfonic acid, is dissolved with 100ml toluene, is heated to 100 DEG C, is reacted 15 hours；Sample point plate, display is surplus without intermediate S2-1 Remaining, reaction is complete；After reaction terminates, into reaction system, addition saturated sodium carbonate solution is quenched, and is extracted with ethyl acetate, point Vacuum rotary steam is to without cut after liquid, organic phase anhydrous sodium sulfate drying, and gained crude product crosses neutral silica gel post, obtains intermediate S3-1, HPLC purity 99.1%, yield 58.1%.
Elementary analysis structure (molecular formula C21H16O2)：Theoretical value C, 83.98；H,5.37；O,10.65；Test value：C, 83.97；H,5.36；O,10.67.ESI-MS(m/z)(M+)：Theoretical value 300.12, measured value is 300.33.
(4) 0.15mol intermediates S3-1,30ml acetic acid is added in 100mL there-necked flask, is cooled to ice salt bath 0℃；9.2ml (0.18mol) bromine for being dissolved in 10ml glacial acetic acid is added dropwise into reaction system at 0 DEG C, is warmed to room temperature, stirs Mix 5h；Sample point plate, display intermediate S3-1 is remaining, and reaction is complete；After reaction terminates, sodium carbonate liquor is added into reaction solution Neutralize, extracted with dichloromethane, is layered, take organic phase, dry filter, filtrate decompression rotates to without cut, crosses silicagel column, obtain Intermediate S4-1, HPLC purity 98.9%, yield 58.3%.
Elementary analysis structure (molecular formula C21H15BrO2)：Theoretical value C, 66.51；H,3.99；Br,21.07；O,8.44；Survey Examination value：C,66.50；H,3.98；Br,21.06；O,8.46.ESI-MS(m/z)(M+)：Theoretical value 378.03, measured value is 378.38。
(5) 250ml there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.08mol intermediates S4-1,40ml tetrahydrochysene furan Dissolving of muttering is complete, is cooled to -78 DEG C, and the tetrahydrofuran that 60mL 1.6mol/L n-BuLis are then added into reaction system is molten Liquid, reacts at -78 DEG C and 0.096mol triisopropyl borate esters is added after 3h, react 2h, reaction system then risen into 0 DEG C, plus Enter 50mL 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, add ether extraction, extract adds anhydrous magnesium sulfate and dried, Revolving, is recrystallized with alcohol solvent, obtains intermediate O1, purity 99.2%, yield 57.3%.
Elementary analysis structure (molecular formula C21H17BO4)：Theoretical value C, 73.29；H,4.98；B,3.14；O,18.59；Test Value：C,73.28；H,4.97；B,3.17；O,18.58.ESI-MS(m/z)(M+)：Theoretical value 344.12, measured value is 344.44。
The synthesis of intermediate II -1 is divided into five steps：Raw material A bromination formation intermediate S1；In intermediate S1 and raw material B synthesis Mesosome S2；Intermediate S2 is through annulation formation intermediate S3；Intermediate S3 brominations formation intermediate S4；Finally by intermediate S4 With triisopropyl borate ester synthetic intermediate II-1, concrete structure is as shown in table 2.
Table 2
b2:The synthesis of intermediate II -2 (X is sulphur atom):
(1) weigh raw material C to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and slowly In the acetic acid solution for being added dropwise to raw material C, 5h is stirred at room temperature, sample point plate, display raw material C is remaining, and reaction is complete；Reaction terminates Afterwards, alkali lye being added into reaction solution to neutralize, being extracted with dichloromethane, be layered, take organic phase to filter, filtrate decompression, which is rotated to nothing, to be evaporated Point, silicagel column is crossed, intermediate S5 is obtained；The mol ratio of the raw material C and bromine is 1:1~1.5；
(2) intermediate S5 and raw material D are weighed, is 1.5~3.0 with volume ratio:1 toluene alcohol mixed solvent dissolving；Again Add Na2CO3The aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by above-mentioned mixed solution at 95~100 DEG C, stirring reaction 10 ~24 hours, room temperature, filtering reacting solution are subsequently cooled to, filtrate revolving crosses silicagel column, obtains intermediate S10；The raw material D and intermediate S5 mol ratio is 1:1.5~3.0；Pd(PPh3)4Mol ratio with raw material D is 0.006~0.02:1, Na2CO3 Mol ratio with raw material D is 2.0~3.0:1；
(3) under nitrogen protection, intermediate S6 and cesium carbonate are weighed, is dissolved with DMSO, 140~150 DEG C, reaction are heated to 8~12 hours；Sample point plate, display is remaining without intermediate S6, and reaction is complete；Reaction system is cooled to room temperature, saturation is added Sodium chloride solution, be extracted with ethyl acetate, point liquid, organic phase anhydrous sodium sulfate drying, vacuum rotary steam, gained crude product mistake Neutral silica gel post, obtains intermediate S7；The intermediate S6 is 1 with the mol ratio to cesium carbonate:1~1.5；
(4) weigh intermediate S7 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Weigh bromine to be dissolved in glacial acetic acid, and delay Slowly it is added dropwise in intermediate S7 acetic acid solution, 5h is stirred at room temperature, sample point plate, display intermediate S7 is remaining, and reaction is complete；Instead After should terminating, alkali lye neutralization is added into reaction solution, is extracted with dichloromethane, is layered, takes organic phase to filter, filtrate decompression revolving To without cut, silicagel column is crossed, intermediate S8 is obtained；The mol ratio of the intermediate S7 and bromine is 1:1~1.5；
(5) under nitrogen protection, weigh intermediate S8 to be dissolved in tetrahydrofuran, be cooled to -78 DEG C, then to reaction system The tetrahydrofuran solution of middle addition 1.6mol/L n-BuLis, triisopropyl borate ester is added after reacting 3h at -78 DEG C, is reacted 2h, then rises to 0 DEG C by reaction system, adds 2mol/L hydrochloric acid solutions, stirs 3h, and reaction is complete, adds ether extraction, extraction Liquid adds anhydrous magnesium sulfate and dried, revolving, is recrystallized with alcohol solvent, obtains intermediate II -2；The intermediate S8 and positive fourth The mol ratio of base lithium is 1:1~1.5；The mol ratio of the intermediate S8 and triisopropyl borate ester are 1:1~1.5.
The synthesis of intermediate II -2 is divided into five steps：Raw material C brominations formation intermediate S5；In intermediate S5 and raw material D synthesis Mesosome S6；Intermediate S6 is through annulation formation intermediate S7；Intermediate S7 brominations formation intermediate S8；Finally by intermediate S8 With triisopropyl borate ester synthetic intermediate II-2, concrete structure is as shown in table 3.
Table 3
B. (the C of intermediate II -31-10Straight or branched alkyl substitution alkylidene or aryl substitution alkylidene) synthesis
(1) raw material E and raw material F are weighed, is 1.5~3.0 with volume ratio:1 toluene alcohol mixed solvent dissolving；Add Na2CO3The aqueous solution, Pd (PPh3)4；Under nitrogen protection, by above-mentioned mixed solution at 95~100 DEG C, stirring reaction 10~24 Hour, room temperature, filtering reacting solution are subsequently cooled to, filtrate revolving crosses silicagel column, obtains intermediate S9；The raw material F and original The mol ratio for expecting E is 1:1.5~3.0；Pd(PPh3)4Mol ratio with raw material F is 0.006~0.02:1, Na2CO3With raw material F Mol ratio be 2.0~3.0:1；
(2) under nitrogen protection, intermediate S9 is weighed, tetrahydrofuran stirring and dissolving is used；Mixed solution is dropped with ice salt bath The tetrahydrofuran solution of the corresponding grignard reagent of brand-new is slowly added dropwise to 0 DEG C in temperature, reacts at room temperature 6~12 hours, sample point plate, Display is remaining without intermediate S10, and reaction is complete；Naturally place to room temperature, filtering, filtrate carries out vacuum rotary steam to without cut, mistake Neutral silica gel post, obtains intermediate S10；The mol ratio of the intermediate S9 and grignard reagent are 1:2~4；
(3) under nitrogen protection, intermediate S10 is weighed, is 1 with volume ratio:2.0~4.0 dense H3PO4With the mixing of water Liquid is reacted at room temperature 6~12 hours, sample point plate as solvent, dissolving, and display is remaining without intermediate S2, and reaction is complete；Add The NaOH aqueous solution is neutralized to pH=7, adds dichloromethane extraction, and layering takes organic phase to filter, and filtrate decompression, which is rotated to nothing, to be evaporated Point, neutral silica gel post is crossed, intermediate S11 is obtained；The mol ratio of the intermediate S10 and concentrated phosphoric acid is 1:3~6；
(4) weigh intermediate S11 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and It is slowly added dropwise into intermediate S11 acetic acid solution, 5h is stirred at room temperature, sample point plate, display intermediate S11 is remaining, has reacted Entirely；After reaction terminates, alkali lye neutralization is added into reaction solution, is extracted with dichloromethane, is layered, takes organic phase to filter, filtrate subtracts Pressure revolving crosses silicagel column, obtains intermediate S12 to without cut；The mol ratio of the intermediate S11 and bromine is 1:1~1.5；
(5) under nitrogen protection, weigh intermediate S12 to be dissolved in tetrahydrofuran, be cooled to -78 DEG C, then to reactant The tetrahydrofuran solution of 1.6mol/L n-BuLis is added in system, triisopropyl borate ester is added after reacting 3h at -78 DEG C, is reacted 2h, then rises to 0 DEG C by reaction system, adds 2mol/L hydrochloric acid solutions, stirs 3h, and reaction is complete, adds ether extraction, extraction Liquid adds anhydrous magnesium sulfate and dried, revolving, is recrystallized with alcohol solvent, obtains intermediate II -3；The intermediate S12 and positive fourth The mol ratio of base lithium is 1:1~1.5；The mol ratio of the intermediate S12 and triisopropyl borate ester are 1:1~1.5.
The synthesis of intermediate II -3 is divided into five steps：By raw material E and raw material F synthetic intermediates S9；Intermediate S9 and form examination Agent generation intermediate S10；Intermediate S10 cyclization generation intermediates S11；Intermediate S11 brominations formation intermediate S12；It is last by Intermediate S12 and triisopropyl borate ester synthetic intermediate II-3, concrete structure is as shown in table 4.
Table 4
b1:The synthesis of intermediate II -4 (X is the tertiary amine groups that aryl replaces)
(1) raw material G and raw material H are weighed, is 1.5~3.0 with volume ratio:1 toluene alcohol mixed solvent dissolving；Add Na2CO3The aqueous solution, Pd (PPh3)4；Under nitrogen protection, by above-mentioned mixed solution at 95~100 DEG C, stirring reaction 10~24 Hour, room temperature, filtering reacting solution are subsequently cooled to, filtrate revolving crosses silicagel column, obtains intermediate S13；The raw material H with Raw material G mol ratio is 1:1.5~3.0；Pd(PPh3)4Mol ratio with raw material H is 0.006~0.02:1, Na2CO3With raw material H mol ratio is 2.0~3.0:1；
(2) under nitrogen protection, intermediate S13 prepared by previous step is dissolved in o-dichlorohenzene, adds triphenylphosphine, Stirring reaction 12~16 hours at 170~190 DEG C, reaction is cooled to room temperature after terminating, and filters, filtrate decompression revolving, excessively neutral Silicagel column, obtains intermediate S14；The intermediate S13 is 1 with triphenylphosphine mol ratio:1~2；
(3) under nitrogen protection, intermediate S14, raw material J, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, Stirred and mixed with toluene, be heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, display is surplus without intermediate S14 Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate S15；The intermediate S14 and raw material J mol ratio is 1:1~2；The Pd2(dba)3Mol ratio with intermediate S14 is 0.006~0.02:1, the tri-butyl phosphine and intermediate S14 mol ratio are 0.006~0.02:1；The sodium tert-butoxide with Intermediate S14 mol ratio is 2.0~3.0:1；
(4) weigh intermediate S15 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and It is slowly added dropwise into intermediate S15 acetic acid solution, 5h is stirred at room temperature, sample point plate, display intermediate S15 is remaining, has reacted Entirely；After reaction terminates, alkali lye neutralization is added into reaction solution, is extracted with dichloromethane, is layered, takes organic phase to filter, filtrate subtracts Pressure revolving crosses silicagel column, obtains intermediate S16 to without cut；The mol ratio of the intermediate S15 and bromine is 1:1~1.5；
(5) under nitrogen protection, weigh intermediate S16 to be dissolved in tetrahydrofuran, be cooled to -78 DEG C, then to reactant The tetrahydrofuran solution of 1.6mol/L n-BuLis is added in system, triisopropyl borate ester is added after reacting 3h at -78 DEG C, is reacted 2h, then rises to 0 DEG C by reaction system, adds 2mol/L hydrochloric acid solutions, stirs 3h, and reaction is complete, adds ether extraction, extraction Liquid adds anhydrous magnesium sulfate and dried, revolving, is recrystallized with alcohol solvent, obtains intermediate II -4；The intermediate S16 and positive fourth The mol ratio of base lithium is 1:1~1.5；The mol ratio of the intermediate S16 and triisopropyl borate ester are 1:1~1.5.
The synthesis of intermediate II -4 is divided into five steps：By raw material G and raw material H synthetic intermediates S13；Intermediate S13 is through cyclization Reaction forms intermediate S14；Intermediate S14 and raw material J synthetic intermediates S15；Intermediate S15 brominations formation intermediate S16；Most Afterwards by intermediate S16 and triisopropyl borate ester synthetic intermediate II-4, concrete structure is as shown in table 5.
Table 5
Embodiment 2：The synthesis of compound 4：
250mL there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediates M1,0.015mol raw material O1, (90ml toluene, 45ml ethanol) is dissolved with mixed solvent, 0.03mol Na are then added2CO3The aqueous solution (2M), leads to nitrogen gas stirring 1 Hour, then add 0.0001mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is complete.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, purity 99.5%, yield 77.7%.Elementary analysis structure (molecular formula C46H32O2)：Theoretical value C, 89.58；H,5.23；O,5.19；Test value：C,89.57；H,5.25；O,5.18.ESI-MS(m/z) (M+)：Theoretical value 616.24, measured value is 616.51.
Embodiment 3：The synthesis of compound 14：
250ml there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediates M2,0.015mol raw material O2, (90ml toluene, 45ml ethanol) is dissolved with mixed solvent, 0.03mol Na are then added2CO3The aqueous solution (2M), leads to nitrogen gas stirring 1 Hour, then add 0.0001mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is complete.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, purity 98.7%, yield 74.4%.Elementary analysis structure (molecular formula C43H34O)：Theoretical value C, 91.13；H,6.05；O,2.82；Test value：C,91.14；H,6.03；O,2.83.ESI-MS(m/z) (M+)：Theoretical value 566.26, measured value is 566.45.
Embodiment 4：The synthesis of compound 25：
250ml there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediates M2,0.015mol raw material O3, (90ml toluene, 45ml ethanol) is dissolved with mixed solvent, 0.03mol Na are then added2CO3The aqueous solution (2M), leads to nitrogen gas stirring 1 Hour, then add 0.0001mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is complete.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, purity 99.1%, yield 73.4%.Elementary analysis structure (molecular formula C53H38O)：Theoretical value C, 92.14；H,5.54；O,2.32；Test value：C,92.15；H,5.55；O,2.30.ESI-MS(m/z) (M+)：Theoretical value 690.29, measured value is 691.52.
Embodiment 5：The synthesis of compound 37：
The preparation method be the same as Example 3 of compound 37, difference is to replace intermediate M2 with using intermediate M1 Mesosome P1 replaces intermediate O2.Elementary analysis structure (molecular formula C46H32OS)：Theoretical value C, 87.31；H,5.10；O,2.53；S, 5.07；Test value：C,87.32；H,5.11；O,2.51；S,5.06.ESI-MS(m/z)(M+)：Theoretical value 632.22, actual measurement It is worth for 632.48.
Embodiment 6：The synthesis of compound 44：
The preparation method be the same as Example 3 of compound 44, difference is to replace intermediate M2 with using intermediate M3 Mesosome P2 replaces intermediate O2.Elementary analysis structure (molecular formula C44H31NOS)：Theoretical value C, 84.99；H,5.03；N,2.25； O,2.57；S,5.16；Test value：C,84.98；H,5.05；N,2.24；O,2.56；S,5.17.ESI-MS(m/z)(M+)：It is theoretical It is worth for 621.21, measured value is 621.45.
Embodiment 7：The synthesis of compound 50：
The preparation method be the same as Example 3 of compound 50, difference is to replace intermediate O2 using intermediate P3.Element Analytical structure (molecular formula C46H33NS)：Theoretical value C, 87.44；H,5.26；N,2.22；S,5.07；Test value：C,87.43；H, 5.27；N,2.24；S,5.06.ESI-MS(m/z)(M+)：Theoretical value 631.23, measured value is 631.47.
Embodiment 8：The synthesis of compound 62：
The preparation method be the same as Example 3 of compound 62, difference is to replace intermediate M2 with using intermediate M4 Mesosome Q1 replaces intermediate O2.Elementary analysis structure (molecular formula C51H38S)：Theoretical value C, 89.70；H,5.61；S,4.70；Survey Examination value：C,89.71；H,5.62；S,4.67.ESI-MS(m/z)(M+)：Theoretical value 682.27, measured value is 682.61.
Embodiment 9：The synthesis of compound 67：
The preparation method be the same as Example 3 of compound 67, difference is to replace intermediate M2 with using intermediate M5 Mesosome Q2 replaces intermediate O2.Elementary analysis structure (molecular formula C52H44)：Theoretical value C, 93.37；H,6.63；Test value：C, 93.35；H,6.65.ESI-MS(m/z)(M+)：Theoretical value 668.34, measured value is 668.63.
Embodiment 10：The synthesis of compound 79：
The preparation method be the same as Example 3 of compound 79, difference is to replace intermediate O2 using intermediate Q3.Element Analytical structure (molecular formula C53H38O)：Theoretical value C, 92.14；H,5.54；O,2.32；Test value：C,92.13；H,5.53；O, 2.34。ESI-MS(m/z)(M+)：Theoretical value 690.29, measured value is 690.63.
Embodiment 11：The synthesis of compound 90：
The preparation method be the same as Example 3 of compound 90, difference is to replace intermediate O2 using intermediate R1.Element Analytical structure (molecular formula C46H33NO)：Theoretical value C, 89.73；H,5.40；N,2.27；O,2.60；Test value：C,89.72；H, 5.41；N,2.24；O,2.63.ESI-MS(m/z)(M+)：Theoretical value 615.26, measured value is 615.56.
Embodiment 12：The synthesis of compound 91：
The preparation method be the same as Example 3 of compound 91, difference is to replace intermediate M2 with using intermediate M5 Mesosome R2 replaces intermediate O2.Elementary analysis structure (molecular formula C52H37NO)：Theoretical value C, 90.27；H,5.39；N,2.02；O, 2.31；Test value：C,90.26；H,5.40；N,2.01；O,2.33.ESI-MS(m/z)(M+)：Theoretical value 691.29, actual measurement It is worth for 691.58.
Embodiment 13：The synthesis of compound 97：
The preparation method be the same as Example 3 of compound 97, difference is to replace intermediate O2 using intermediate R3.Element Analytical structure (molecular formula C46H33NO)：Theoretical value C, 89.73；H,5.40；N,2.27；O,2.60；Test value：C,89.71；H, 5.41；N,2.28；O,2.61.ESI-MS(m/z)(M+)：Theoretical value 615.26, measured value is 615.54.
Embodiment 14：The synthesis of compound 98：
The preparation method be the same as Example 3 of compound 98, difference is to replace intermediate O2 using intermediate R4.Element Analytical structure (molecular formula C46H33NO)：Theoretical value C, 89.73；H,5.40；N,2.27；O,2.60；Test value：C,89.71；H, 5.41；N,2.26；O,2.62.ESI-MS(m/z)(M+)：Theoretical value 615.26, measured value is 615.57.
Embodiment 15：The synthesis of compound 102：
The preparation method be the same as Example 3 of compound 102, difference is to replace intermediate O2 using intermediate R5.Member Plain analytical structure (molecular formula C49H39N)：Theoretical value C, 91.69；H,6.12；N,2.18；Test value：C,91.67；H,6.14；N, 2.19。ESI-MS(m/z)(M+)：Theoretical value 641.31, measured value is 641.67.
Embodiment 16：The synthesis of compound 103：
The preparation method be the same as Example 3 of compound 103, difference is to replace intermediate O2 using intermediate R6.Member Plain analytical structure (molecular formula C49H39N)：Theoretical value C, 91.69；H,6.12；N,2.18；Test value：C,91.68；H,6.13；N, 2.19。ESI-MS(m/z)(M+)：Theoretical value 641.31, measured value is 641.64.
Embodiment 17：The synthesis of compound 108：
The preparation method be the same as Example 3 of compound 108, difference is to replace intermediate O2 using intermediate R7.Member Plain analytical structure (molecular formula C52H38N2)：Theoretical value C, 90.40；H,5.54；N,4.05；Test value：C,90.42；H,5.55；N, 4.03。ESI-MS(m/z)(M+)：Theoretical value 690.30, measured value is 690.58.
Embodiment 18：The synthesis of compound 115：
The preparation method be the same as Example 3 of compound 115, difference is to replace intermediate O2 using intermediate R8.Member Plain analytical structure (molecular formula C46H33NS)：Theoretical value C, 87.44；H,5.26；N,2.22；S,5.07；Test value：C,87.45； H,5.25；N,2.24；S,5.06.ESI-MS(m/z)(M+)：Theoretical value 631.23, measured value is 631.23.
Embodiment 19：The synthesis of compound 124：
The preparation method be the same as Example 3 of compound 124, difference is to replace intermediate O2 using intermediate R9.Member Plain analytical structure (molecular formula C48H31N3S)：Theoretical value C, 84.55；H,4.58；N,6.16；S,4.70；Test value：C,84.54； H,4.59；N,6.15；S,4.72.ESI-MS(m/z)(M+)：Theoretical value 681.22, measured value is 681.49.
Embodiment 20：The synthesis of compound 127：
The preparation method be the same as Example 3 of compound 127, difference is to replace intermediate O2 using intermediate R10.Member Plain analytical structure (molecular formula C56H37NO)：Theoretical value C, 90.90；H,5.04；N,1.89；O,2.16；Test value：C,90.92； H,5.02；N,1.88；O,2.18.ESI-MS(m/z)(M+)：Theoretical value 739.29, measured value is 739.58.
Embodiment 21：The synthesis of compound 134：
The preparation method be the same as Example 3 of compound 134, difference is to replace intermediate O2 using intermediate R11.Member Plain analytical structure (molecular formula C59H43N)：Theoretical value C, 92.51；H,5.66；N,1.83；Test value：C,92.52；H,5.64；N, 1.84。ESI-MS(m/z)(M+)：Theoretical value 765.34, measured value is 765.57.
Embodiment 22：The synthesis of compound 143：
The preparation method be the same as Example 3 of compound 143, difference is to replace intermediate O2 using intermediate R12.Member Plain analytical structure (molecular formula C52H38N2)：Theoretical value C, 90.40；H,5.54；N,4.05；Test value：C,90.41；H,5.52；N, 4.07。ESI-MS(m/z)(M+)：Theoretical value 690.30, measured value is 690.61.
Embodiment 23：The synthesis of compound 148：
The preparation method be the same as Example 3 of compound 148, difference is to replace intermediate O2 using intermediate R13.Member Plain analytical structure (molecular formula C52H37NO)：Theoretical value C, 90.27；H,5.39；N,2.02；O,2.31；Test value：C,90.25； H,5.38；N,2.04；O,2.33.ESI-MS(m/z)(M+)：Theoretical value 691.29, measured value is 691.57.
Embodiment 24：The synthesis of compound 159：
The preparation method be the same as Example 3 of compound 159, difference is to replace intermediate O2 using intermediate R14.Member Plain analytical structure (molecular formula C52H37NO)：Theoretical value C, 90.27；H,5.39；N,2.02；O,2.31；Test value：C,90.26； H,5.40；N,2.03；O,2.31.ESI-MS(m/z)(M+)：Theoretical value 691.29, measured value is 691.63.
Embodiment 25：The synthesis of compound 164：
The preparation method be the same as Example 3 of compound 164, difference is to replace intermediate O2 using intermediate R15.Member Plain analytical structure (molecular formula C52H37NO)：Theoretical value C, 90.27；H,5.39；N,2.02；O,2.31；Test value：C,90.29； H,5.38；N,2.01；O,2.32.ESI-MS(m/z)(M+)：Theoretical value 691.29, measured value is 691.54.
Embodiment 26：The synthesis of compound 168：
The preparation method be the same as Example 3 of compound 168, difference is to replace intermediate O2 using intermediate R16.Member Plain analytical structure (molecular formula C55H43N)：Theoretical value C, 92.01；H,6.04；N,1.95；Test value：C,92.02；H,6.05；N, 1.93。ESI-MS(m/z)(M+)：Theoretical value 717.34, measured value is 717.66.
Embodiment 27：The synthesis of compound 169：
The preparation method be the same as Example 3 of compound 169, difference is to replace intermediate O2 using intermediate R17.Member Plain analytical structure (molecular formula C55H43N)：Theoretical value C, 92.01；H,6.04；N,1.95；Test value：C,92.03；H,6.03；N, 1.94。ESI-MS(m/z)(M+)：Theoretical value 717.34, measured value is 717.61.
Embodiment 28：The synthesis of compound 173：
The preparation method be the same as Example 3 of compound 173, difference is to replace intermediate O2 using intermediate R18.Member Plain analytical structure (molecular formula C55H43N)：Theoretical value C, 92.01；H,6.04；N,1.95；Test value：C,92.02；H,6.02；N, 1.96。ESI-MS(m/z)(M+)：Theoretical value 717.34, measured value is 717.58.
Embodiment 29：The synthesis of compound 182：
The preparation method be the same as Example 3 of compound 182, difference is to replace intermediate O2 using intermediate R19.Member Plain analytical structure (molecular formula C58H42N2)：Theoretical value C, 90.83；H,5.52；N,3.65；Test value：C,90.85；H,5.51； N,3.64。ESI-MS(m/z)(M+)：Theoretical value 766.33, measured value is 766.58.
Embodiment 30：The synthesis of compound 185：
The preparation method be the same as Example 3 of compound 185, difference is to replace intermediate O2 using intermediate R20.Member Plain analytical structure (molecular formula C48H35N)：Theoretical value C, 92.12；H,5.64；N,2.24；Test value：C,92.11；H,5.66；N, 2.23。ESI-MS(m/z)(M+)：Theoretical value 625.28, measured value is 625.49.
The organic compound of the present invention is used in luminescent device, can be as electronic blocking layer material, can also conduct Luminescent layer Subjective and Objective materials'use.To the compounds of this invention 4,14,25,37,50,67,79,90,91,97,98,102,103, 108th, 115,127,134,143,148,159,164,168,169,173,182,185 carry out respectively T1 energy levels, hot property, The test of HOMO energy levels, testing result is as shown in table 6.
Table 6
Note：Triplet T1 is the F4600 XRFs test by Hitachi, and the test condition of material is 2*10-5's Toluene solution；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimeters) Determine, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in Japanese Shimadzu Corporation TGA-50H thermogravimetric analyzers on be measured, nitrogen flow is 20mL/min；Highest occupied molecular orbital HOMO energy levels be by Ionizing energy test system (IPS3) is tested, and is tested as atmospheric environment.
From upper table data, organic compound of the invention has different HOMO energy levels, can be applied to different work( Ergosphere, the present invention has higher triplet and higher heat endurance using fluorenes as the organic compound of core so that institute The OLED efficiency containing organic compound of the present invention and life-span made gets a promotion.
The OLED material of the invention synthesized is described in detail in device below by way of device embodiments 1~26 and device comparative example 1 Application effect in part.Device embodiments 2~26 of the present invention, device comparative example 1 device compared with device embodiments 1 Manufacture craft it is identical, and employed identical baseplate material and electrode material, the thickness of electrode material are also kept Unanimously, except that device embodiments 2~13 are to use material of the present invention as electronic barrier layer application；Device is implemented The material of main part of luminescent layer in 14~26 pairs of devices of example is converted.The performance test results such as table of each embodiment obtained device Shown in 7.
Device embodiments 1：As shown in figure 1, a kind of electroluminescent device, its preparation process includes：A) transparency carrier is cleaned Ito anode layer 2 on layer 1, is cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate, then in plasma clean respectively Handled 2 minutes in device；B) on ito anode layer 2, hole injection layer material HAT-CN, thickness are deposited by vacuum evaporation mode For 10nm, this layer is used as hole injection layer 3；C) on hole injection layer 3, hole mobile material is deposited by vacuum evaporation mode NPB, thickness is 60nm, and the layer is hole transmission layer 4；D) on hole transmission layer 4, electronics is deposited by vacuum evaporation mode and hindered Barrier material the compounds of this invention 90, thickness is 20nm, and the layer is electronic barrier layer 5；E) hair is deposited on electronic barrier layer 5 Photosphere 6, using CBP as material of main part, Ir (ppy)3It is used as dopant material, Ir (ppy)3Mass ratio with CBP is 10:90, it is thick Spend for 30nm；F) on luminescent layer 6, electron transport material TPBI is deposited by vacuum evaporation mode, thickness is 40nm, this layer Organic material is used as hole barrier/electron transfer layer 7；G) on hole barrier/electron transfer layer 7, vacuum evaporation electricity Sub- implanted layer LiF, thickness is 1nm, and the layer is electron injecting layer 8；H) on electron injecting layer 8, vacuum evaporation negative electrode Al (100nm), the layer is negative electrode reflection electrode layer 9.
The molecular structural formula of associated materials is as follows：
Device embodiments 2：The difference of the present embodiment and device embodiments 1 is：The electronics resistance of electroluminescent device Barrier material is the compounds of this invention 91.Device embodiments 3：The difference of the present embodiment and device embodiments 1 is：It is electroluminescent The electronic blocking layer material of luminescent device is the compounds of this invention 97.Device embodiments 4：The present embodiment and device embodiments 1 Difference is：The electronic blocking layer material of electroluminescent device is the compounds of this invention 98.Device embodiments 5：This implementation Example and the difference of device embodiments 1 are：The electronic blocking layer material of electroluminescent device is the compounds of this invention 108. Device embodiments 6：The difference of the present embodiment and device embodiments 1 is：The electronic blocking layer material of electroluminescent device For the compounds of this invention 115.Device embodiments 7：The difference of the present embodiment and device embodiments 1 is：Electroluminescent cell The electronic blocking layer material of part is the compounds of this invention 127.Device embodiments 8：The present embodiment it is different from device embodiments 1 it Be in：The electronic blocking layer material of electroluminescent device is the compounds of this invention 143.Device embodiments 9：The present embodiment and device The difference of part embodiment 1 is：The electronic blocking layer material of electroluminescent device is the compounds of this invention 148.Device is real Apply example 10：The difference of the present embodiment and device embodiments 1 is：The electronic blocking layer material of electroluminescent device is this hair Bright compound 159.Device embodiments 11：The difference of the present embodiment and device embodiments 1 is：The electricity of electroluminescent device Sub- barrier material is the compounds of this invention 164.Device embodiments 12：The difference of the present embodiment and device embodiments 1 exists In：The electronic blocking layer material of electroluminescent device is the compounds of this invention 182.Device embodiments 13：The present embodiment and device The difference of embodiment 1 is：The electronic blocking layer material of electroluminescent device is the compounds of this invention 185.
Device embodiments 14：The difference of the present embodiment and device embodiments 1 is：The electronics resistance of electroluminescent device Barrier material is NPB, and the luminescent layer material of main part of electroluminescent device is changed into the compounds of this invention 102, and dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 102 is 10:90.Device embodiments 15：The present embodiment and device embodiments 1 Difference is：The electronic blocking layer material of electroluminescent device is NPB, and the luminescent layer material of main part of electroluminescent device becomes For the compounds of this invention 103, dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 103 is 10:90.Device is real Apply example 16：The difference of the present embodiment and device embodiments 1 is：The electronic blocking layer material of electroluminescent device is NPB, The luminescent layer material of main part of electroluminescent device is changed into the compounds of this invention 134, and dopant material is Ir (ppy)3, Ir (ppy)3With The mass ratio of compound 134 is 10:90.Device embodiments 17：The difference of the present embodiment and device embodiments 1 is：Electricity The electronic blocking layer material of electroluminescence device is NPB, and the luminescent layer material of main part of electroluminescent device is changed into the compounds of this invention 168, dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 168 is 10:90.Device embodiments 18：This implementation Example and the difference of device embodiments 1 are：The electronic blocking layer material of electroluminescent device is NPB, electroluminescent device Luminescent layer material of main part be changed into the compounds of this invention 169, dopant material is Ir (ppy)3, Ir (ppy)3With the matter of compound 169 Amount is than being 10:90.Device embodiments 19：The difference of the present embodiment and device embodiments 1 is：The electricity of electroluminescent device Sub- barrier material is NPB, and the luminescent layer material of main part of electroluminescent device is changed into the compounds of this invention 173, and dopant material is Ir(ppy)3, Ir (ppy)3Mass ratio with compound 173 is 10:90.Device embodiments 20：The present embodiment and device embodiments 1 Difference be：The electronic blocking layer material of electroluminescent device is NPB, the luminescent layer material of main part of electroluminescent device It is changed into the compounds of this invention 4 and compound GHN, dopant material is Ir (ppy)3, compound 4, GHN and Ir (ppy)3Three's mass Than for for 60:30:10.Device embodiments 21：The difference of the present embodiment and device embodiments 1 is：Electroluminescent device Electronic blocking layer material be NPB, the luminescent layer material of main part of electroluminescent device is changed into the compounds of this invention 14 and compound GHN, dopant material is Ir (ppy)3, compound 14, GHN and Ir (ppy)3Three's mass ratio is 60:30:10.Device embodiments 22：The difference of the present embodiment and device embodiments 1 is：The electronic blocking layer material of electroluminescent device is NPB, electroluminescent The luminescent layer material of main part of luminescent device is changed into the compounds of this invention 25 and compound GHN, and dopant material is Ir (ppy)3, chemical combination Thing 25, GHN and Ir (ppy)3Three's mass ratio is 60:30:10.Device embodiments 23：The present embodiment and device embodiments 1 Difference is：The electronic blocking layer material of electroluminescent device is NPB, and the luminescent layer material of main part of electroluminescent device becomes For the compounds of this invention 37 and compound GHN, dopant material is Ir (ppy)3, compound 37, GHN and Ir (ppy)3Three's mass Than for for 60:30:10.The difference of the present embodiment of device embodiments 24 and device embodiments 1 is：Electroluminescent device Electronic blocking layer material is NPB, and the luminescent layer material of main part of electroluminescent device is changed into the compounds of this invention 50 and compound GHN, dopant material is Ir (ppy)3, compound 50, GHN and Ir (ppy)3Three's mass ratio is 60:30:10.Device embodiments 25：The difference of the present embodiment and device embodiments 1 is：The electronic blocking layer material of electroluminescent device is NPB, electroluminescent The luminescent layer material of main part of luminescent device is changed into the compounds of this invention 67 and compound GHN, and dopant material is Ir (ppy)3, chemical combination Thing 67, GHN and Ir (ppy)3Three's mass ratio is 60:30:10.Device embodiments 26：The present embodiment and device embodiments 1 Difference is：The electronic blocking layer material of electroluminescent device is NPB, and the luminescent layer material of main part of electroluminescent device becomes For the compounds of this invention 79 and compound GHN, dopant material is Ir (ppy)3, compound 79, GHN and Ir (ppy)3Three's mass Than for for 60:30:10.
Device comparative example 1：
The difference of the present embodiment and device embodiments 1 is：The electronic blocking layer material of electroluminescent device is NPB, the luminescent layer material of main part of electroluminescent device is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3With CBP mass ratio is 10:90.After the making of above-mentioned electroluminescent device, the current efficiency of measurement device and life-span, its result are shown in Shown in table 7.
Table 7
Note：Life-span test system is owner of the present invention and the OLED life test of Shanghai University's joint research Instrument.
It can be seen that the machine compound of the present invention using fluorenes as core can be applied to OLED luminescent devices by the result of table 7 Make, and compared with device comparative example 1, either the change more larger than the acquisition of known OLED material of efficiency or life-span, special It is not the larger lifting of the life time decay acquisition of device.
OLED prepared by further material of the present invention can be kept for the long-life at high temperature, by device embodiments 1~26 and device comparative example 1 carry out high temperature driven life tests at 85 DEG C, acquired results are as shown in table 8.
Table 8
It was found from the data of table 8, device embodiments 1~26 are the device architecture that material of the present invention and known materials are arranged in pairs or groups, Compared with device comparative example 1, under high temperature, the OLED that the present invention is provided has the driving life-span well.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.

Claims (8)

1. a kind of organic compound using fluorenes as core, it is characterised in that the structure of the organic compound such as formula (1) institute Show：
In formula (1), Ar is expressed as phenyl, dibiphenylyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, thiophene One kind in base, pyridine radicals, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical；
In formula (1), R is expressed as structure shown in formula (2)；
In formula (2), X is expressed as oxygen atom, sulphur atom, C1-10The alkylidene of straight or branched alkyl substitution, the Asia of aryl substitution One kind in alkyl, the tertiary amine groups of alkyl or aryl substitution；
In formula (2), R1It is expressed as the structure shown in formula (3)；
Wherein, a is selected fromX1、X2Independently be expressed as oxygen atom, sulphur atom, C1-10Straight or branched alkane One kind in the tertiary amine groups that alkylidene, the alkylidene of aryl substitution, the alkyl or aryl of base substitution replace；
Formula (3) passes through CL1-CL2Key, CL2-CL3Key or CL3-CL4Key is connected with formula (2).
2. organic compound according to claim 1, it is characterised in that the formula (2) is expressed as：
In any one.
3. organic compound according to claim 1, it is characterised in that the concrete structure formula of the organic compound is：
In any one.
4. the preparation method of any one of a kind of claims 1 to 3 organic compound, it is characterised in that sent out in preparation process Raw reaction equation is：
Specifically preparation method is：Intermediate compound I and intermediate II are weighed, is 1.5~3 with volume ratio:1 toluene alcohol mixed solvent Dissolving；Add Na2CO3The aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature Reacted 10~24 hours at 90~110 DEG C of degree, cooling, filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；
The mol ratio of the intermediate compound I and intermediate II is 1:1.0~1.5；Pd(PPh3)4Mol ratio with intermediate compound I is 0.006~0.02:1, Na2CO3Mol ratio with intermediate compound I is 2.0~3.0:1.
5. a kind of organic compound using fluorenes as core as described in any one of claims 1 to 3 is used to prepare organic electroluminescence hair Optical device.
6. a kind of organic electroluminescence device, it is characterised in that the organic electroluminescence device includes at least one layer of functional layer Contain the organic compound using fluorenes as core described in any one of claims 1 to 3.
7. a kind of organic electroluminescence device, including electronic barrier layer, it is characterised in that the electronic blocking layer material is right It is required that the organic compound using fluorenes as core described in 1~3 any one.
8. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that the luminescent layer, which contains claims 1 to 3, appoints The organic compound using fluorenes as core described in one.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107188873A (en) * 2017-06-12 2017-09-22 长春海谱润斯科技有限公司 A kind of phosphorescent light body material and organic luminescent device containing spirane structure
CN107513034A (en) * 2017-09-29 2017-12-26 江苏三月光电科技有限公司 A kind of dimethylanthracene class organic compound and its application
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CN107602470A (en) * 2017-09-29 2018-01-19 江苏三月光电科技有限公司 A kind of dimethylanthracene class organic compound and its application in OLED
CN107652297A (en) * 2017-09-29 2018-02-02 江苏三月光电科技有限公司 A kind of oxa anthracenes organic compound and its application in OLED
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CN109575012A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of organic compound and its application containing fluorenes and pyridine diindyl
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CN109824577A (en) * 2017-11-23 2019-05-31 江苏三月光电科技有限公司 A kind of Spirofluorene derivative species organic compound and its application in OLED device
CN111244310A (en) * 2018-11-29 2020-06-05 固安鼎材科技有限公司 Organic electroluminescent device and organic electroluminescent display device
CN112010866A (en) * 2020-09-07 2020-12-01 京东方科技集团股份有限公司 Dioxin compound and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140130297A (en) * 2013-04-30 2014-11-10 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
CN104471021A (en) * 2012-06-04 2015-03-25 株式会社P&Htech Novel organic electroluminescent element compound and organic electroluminescent element comprising same
CN106432158A (en) * 2016-09-19 2017-02-22 江苏三月光电科技有限公司 Organic light emitting compound material and application thereof
US20170141321A1 (en) * 2015-11-12 2017-05-18 Sfc Co., Ltd. Organic light-emitting diode with high efficiency

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104471021A (en) * 2012-06-04 2015-03-25 株式会社P&Htech Novel organic electroluminescent element compound and organic electroluminescent element comprising same
KR20140130297A (en) * 2013-04-30 2014-11-10 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
US20170141321A1 (en) * 2015-11-12 2017-05-18 Sfc Co., Ltd. Organic light-emitting diode with high efficiency
CN106432158A (en) * 2016-09-19 2017-02-22 江苏三月光电科技有限公司 Organic light emitting compound material and application thereof

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* Cited by examiner, † Cited by third party
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