CN107337680B - It is a kind of using fluorenes as the organic compound of core and its application in OLED device - Google Patents

It is a kind of using fluorenes as the organic compound of core and its application in OLED device Download PDF

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CN107337680B
CN107337680B CN201710580301.XA CN201710580301A CN107337680B CN 107337680 B CN107337680 B CN 107337680B CN 201710580301 A CN201710580301 A CN 201710580301A CN 107337680 B CN107337680 B CN 107337680B
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compound
organic compound
fluorenes
layer
added
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CN107337680A (en
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唐丹丹
邢宗仁
李崇
张小庆
张兆超
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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 using fluorenes as the organic compound of core and its application in OLED device, the structure of the compound is that fluorenes is connected by carbon-carbon bond with benzo hexatomic ring and ring structure, carbon-carbon bond connection had both improved materials chemistry stability, and in turn avoid the active position of branched group exposed, and entire molecule is a biggish rigid structure, triplet (T1) with higher；And steric hindrance is big, is not easy to rotate, solid space structure is more stable, therefore compound glass transition temperature with higher and molecule thermal stability；In addition, HOMO the and LUMO distributing position of the compounds of this invention is separated from each other, suitable HOMO and lumo energy are made it have；Therefore, after the compounds of this invention is applied to OLED device, the luminous efficiency and service life of device can effectively be promoted.

Description

It is a kind of using fluorenes as the organic compound of core and its application in OLED device
Technical field
The present invention relates to technical field of semiconductors, more particularly, to it is a kind of using fluorenes as the organic compound of core and its Application on OLED.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is very extensive.OLED luminescent device including electrode material film layer and is clipped in different electricity like the structure of sandwich Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together Optical device.OLED luminescent device is as current device, when applying voltage to its two end electrodes, and passes through electric field action organic layer function Can positive and negative charge in film layer when, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity Depending on etc. large scales application field extension, still with actual products application require compare, the luminous efficiency and use of OLED device The performances such as service life also need further to be promoted.Proposing high performance research to OLED luminescent device at present includes: to 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 device mentions It rises, not only needs the innovation from OLED device structure and manufacture craft, constantly study and create with greater need for oled light sulfate ferroelectric functional material Newly, the OLED functional material of higher performance is formulated out.
Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two major classes from purposes, and respectively 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 device, it is desirable that various organic functional materials have good photoelectric properties, For example, as charge transport materials, it is desirable that have good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer has good bipolarity, HOMO/LUMO energy rank appropriate etc..
The oled light sulfate ferroelectric functional material film layer for constituting OLED device includes at least two layers or more structure, applies in industry OLED device structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron-transport A variety of film layers such as layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is injected including at least hole 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, used photoelectric functional material has stronger choosing for the collocation of the OLED device of different structure Selecting property, performance of the identical material in different structure device may also be completely totally different.
Therefore, for the industry application requirement of current OLED device and the different function film layer of OLED device, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, the higher OLED functional material of performance or combination of materials, is just able to achieve the height of device Efficiency, the overall characteristic of long-life and low-voltage.For current OLED shows the actual demand of Lighting Industry, OLED at present The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as the organic of material enterprise development higher performance Functional material is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide it is a kind of using fluorenes as the organic compound of core and Its application on organic electroluminescence device.The compounds of this invention contain it is fluorene structured, glass transition temperature with higher and point Sub- thermal stability, suitable HOMO and lumo energy, higher Eg are optimized by device architecture, can effectively promote OLED device The service life of photoelectric properties and OLED device.Technical scheme is as follows:
It is a kind of using fluorenes as the organic compound of core, shown in the structure of the organic compound such as general formula (1):
In general formula (1), Ar be expressed as phenyl, dibiphenylyl, terphenyl, naphthalene, anthryl, phenanthryl, pyrenyl, furyl, One of thienyl, pyridyl group, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical；
In general formula (1), R points are expressed as structure shown in general formula (2)；
In general formula (2), X1、X2、X3Independently be expressed as oxygen atom, sulphur atom, C1-10Linear or branched alkyl group replaces Alkylidene, one of the tertiary amine groups that replace of the aryl alkylidene, the alkyl or aryl that replace；
In general formula (2),Pass through CL1-CL2Key, CL2-CL3Key or CL3-CL4Key withConnection.
Preferably, the general formula (2) indicates are as follows:
Any one.
Preferably, the concrete structure formula of the organic compound are as follows:
In any one.
The applicant additionally provides a kind of preparation method of organic compound, the reactional equation occurred in preparation process Formula are as follows:
Specifically the preparation method comprises the following steps: weighing intermediate compound I and intermediate II, mixed with the toluene ethyl alcohol that volume ratio is 1.5~3:1 Solvent dissolution；Add Na2CO3Aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in anti- It answers and is reacted 10~24 hours at 90~110 DEG C of temperature, cooling, filtering reacting solution, filtrate revolving crosses silicagel column, obtains target Product；
The molar ratio of the intermediate compound I and intermediate II is 1:1.0~1.5；Pd(PPh3)4Molar ratio with intermediate compound I is 0.006~0.02:1, Na2CO3Molar ratio with intermediate compound I is 2.0~3.0:1.
The applicant additionally provides and is used to prepare organic electroluminescent by the organic compound of core of fluorenes described in one kind Device.The organic electroluminescence device includes described at least one layer of functional layer contains using fluorenes as the organic compound of core.
The applicant additionally provides a kind of organic electroluminescence device, including electronic barrier layer, the electronic barrier layer material Material is described using fluorenes as the organic compound of core.The applicant additionally provides a kind of organic electroluminescence device, including hair Photosphere, the luminescent layer contain described using fluorenes as the organic compound of core.
The present invention is beneficial to be had the technical effect that
The compounds of this invention is using fluorenes as skeleton, and with benzo hexatomic ring and ring structure is connected with carbon-carbon bond, carbon-carbon bond connection Both having improved stability of material, in turn avoid the active position of branched group exposed；Such compound has biggish rigidity in addition to fluorenes Outside, benzo hexatomic ring and ring structure are also the rigid structure of one big pi bond conjugation, and steric hindrance is big, is not easy to rotate, so that this hair The stereochemical structure of bright compound-material is more stable.And the spin density distribution of the compounds of this invention triplet T1 is basic On branch, branch has high T1 energy level, therefore the compounds of this invention equally has high T1 energy level；The compounds of this invention conduct When the electronic barrier layer materials'use of OLED, high T1 energy level can effectively stop energy to pass from luminescent layer to hole transmission layer It passs, reduces energy loss, luminescent layer material of main part energy is made to be sufficiently transmitted to dopant material, to promote material applied to device Luminous efficiency after part.
The structure of organic compound of the invention balances electrons and holes more in the distribution of luminescent layer, appropriate Under HOMO energy level, hole injection and transmission performance are improved；Under suitable lumo energy, and play the work of electronic blocking With combined efficiency of the promotion exciton in luminescent layer；When light emitting functional layer materials'use as OLED luminescent device, fluorenes collocation Branch in the scope of the invention can effectively improve exciton utilization rate and high fluorescent radiation efficiency, reduce the efficiency under high current density It roll-offs, reduces device voltage, improve current efficiency and the service life of device.Organic compound of the invention is in OLED device application When, optimized by device architecture, high membranous layer stability can be kept, can effectively promote the photoelectric properties and OLED of OLED device The service life of device has good application effect and industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；Wherein, 1, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, 4, hole transmission layer 5, electronic barrier layer, 6, luminescent layer, 7, hole barrier/electronics biography Defeated layer, 8, electron injecting layer, 9, cathode reflection electrode layer.
Specific 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, micro catalysis is added Agent I2, it is heated to 40 DEG C of stirrings and is become colorless to solution by yellow, then above-mentioned mixed solution is heated at 60~90 DEG C, stirs Reaction 3~5 hours, no magnesium powder is remaining, fully reacting, generates grignard reagent intermediate V；The molar ratio of the raw material U and Mg is 1:1.0~1.2；I2Molar 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, is stirred to react 10~24 hours, is generated a large amount of white precipitates, then cool to room temperature, add Enter to be saturated NHCl4Alcohol is converted by format salt；After completion of the reaction, ether extracts, and dry revolving crosses silicagel column, obtains slightly yellow The solid tertiary alcohol intermediates W of color；The molar ratio of the 9-Fluorenone and intermediate V are 1:1.0~1.2；
(3) intermediate W is weighed, is dissolved with toluene；48%HBr aqueous solution is slowly added dropwise in mixed solution, 20~25 It is stirred to react at DEG C 15~30 hours, liquid separation after reaction, water phase is extracted with toluene, and organic phase uses anhydrous sodium sulfate after merging It is dry, it filters, filter cake uses ethyl acetate rinse again, and 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 that 20ml corresponds to every 0.01mol intermediate W.
By taking intermediate M1 synthesis as an example:
(1) 0.05mol raw material U1,0.06molMg powder is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL, uses The dissolution of 60ml dry tetrahydrofuran, is added 0.0004mol simple substance I2, it is heated to 40 DEG C of stirrings and is become colorless to solution by yellow, Above-mentioned mixed solution is heated at 80 DEG C, is stirred to react 4 hours, no magnesium powder is remaining, fully reacting, generates among grignard reagent Body V1 is directly carried out in next step without purification.
(2) 0.03mol9- Fluorenone is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL, with the dry tetrahydro of 40ml Furans dissolution, is slowly added dropwise above-mentioned grignard reagent intermediate V1 solution, is heated to reflux 15 hours, generates a large amount of white precipitates, so After be cooled to room temperature, be added saturation NHCl4Alcohol is converted by format salt；After completion of the reaction, ether extracts, and dry revolving crosses silicon Rubber column gel column obtains solid tertiary alcohol intermediates W1, the HPLC purity 99.2% of yellowish, yield 74.7%.
Elemental analysis structure (molecular formula C19H14O): theoretical value C, 88.34；H,5.46；O,6.19；Test value: C, 88.35；H,5.47；O,6.18.ESI-MS(m/z)(M+): theoretical value 258.10, measured value 258.35.
(3) 0.02mol intermediate W1 is added in the there-necked flask of 250mL, is dissolved with 50ml toluene, 48%HBr water is slowly added dropwise Solution (40ml) is stirred to react 24 hours at 25 DEG C, and liquid separation after reaction, water phase is extracted with toluene, after organic phase merges It is dried, is filtered with anhydrous sodium sulfate, filter cake uses ethyl acetate rinse again, and filtrate and flushing liquor are rotated to solvent-free, mistake silica gel Column obtains intermediate M1, HPLC purity 99.4%, yield 73.5%.
Elemental analysis structure (molecular formula C19H13Br): theoretical value C, 71.04；H,4.08；Br,24.88；Test value: C, 71.06；H,4.07；Br,24.87.ESI-MS(m/z)(M+): theoretical value 320.02, measured value 320.33.
Intermediate compound I is prepared with the synthetic method of intermediate M1, 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, specific structure As shown in table 1.
Table 1
B. intermediate II, that is, R-B (OH)2Synthesis:
B1: (the X of intermediate II -13For oxygen atom) synthesis:
(1) it weighs raw material A to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；It weighs bromine 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 contact plate, display is without raw material A residue, fully reacting；Reaction terminates Afterwards, lye is added into reaction solution to neutralize, is extracted with dichloromethane, be layered, organic phase is taken to filter, filtrate decompression, which is rotated to nothing, to be evaporated Point, silicagel column is crossed, intermediate S1 is obtained；The molar ratio of the raw material A and bromine is 1:1~1.5；
(2) intermediate S1 and raw material B are weighed, is dissolved with the toluene alcohol mixed solvent that volume ratio is 1.5~3.0:1；Again Na is added2CO3Aqueous solution, Pd (PPh3)4；Under an inert atmosphere, above-mentioned mixed solution is stirred to react 10 at 95~100 DEG C It~24 hours, then cools to room temperature, filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate S2；The raw material B Molar ratio with intermediate S1 is 1:1.5~3.0；Pd(PPh3)4Molar ratio with raw material B is 0.006~0.02:1, Na2CO3 Molar 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, is heated to 95~100 DEG C, Reaction 10~24 hours；Contact plate is sampled, display is remaining without intermediate S2, fully reacting；After reaction, add into reaction system Enter saturated sodium carbonate solution to be quenched, be extracted with ethyl acetate, liquid separation, organic phase with anhydrous sodium sulfate it is dry after vacuum rotary steam to nothing Fraction, gained crude product cross neutral silica gel column, obtain intermediate S3；The molar ratio of the intermediate S2 and p-methyl benzenesulfonic acid is 1: 1~1.5；
(4) it weighs intermediate S3 to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；It weighs bromine to be dissolved in glacial acetic acid, and delays Slowly it is added dropwise in the acetic acid solution of intermediate S3,5h is stirred at room temperature, sample contact plate, display is remaining without raw material S3, fully reacting；Instead After answering, lye is added into reaction solution and neutralizes, is extracted with dichloromethane, is layered, organic phase is taken to filter, filtrate decompression revolving To no fraction, silicagel column is crossed, intermediate S4 is obtained；The molar ratio of the intermediate S4 and bromine is 1:1~1.5；
(5) under nitrogen protection, it weighs intermediate S4 to be dissolved in tetrahydrofuran, is cooled to -78 DEG C, then to reaction system The middle tetrahydrofuran solution that 1.6mol/L n-BuLi is added, is added triisopropyl borate ester after reacting 3h at -78 DEG C, reacts Then reaction system is risen to 0 DEG C by 2h, 2mol/L hydrochloric acid solution is added, and stirs 3h, and ether extraction, extraction is added in fully reacting Anhydrous magnesium sulfate drying is added in liquid, and revolving is recrystallized with alcohol solvent, obtains intermediate II -1；The intermediate S4 and positive fourth The molar ratio of base lithium is 1:1~1.5；The molar ratio of the intermediate S4 and triisopropyl borate ester is 1:1~1.5.
It is such by taking the synthesis of intermediate O1 as an example:
(1) 0.1mol raw material A 1 is added in the there-necked flask of 250mL, 50ml acetic acid is 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；Contact plate is sampled, display is remaining without raw material A 1, fully reacting, after reaction, is added in sodium carbonate liquor into reaction solution Be extracted with dichloromethane, be layered, take organic phase, dry filter, filtrate decompression is rotated to no fraction, cross silicagel column, is obtained Mesosome S1-1, HPLC purity 99.4%, yield 68.4%.
Elemental analysis structure (molecular formula C15H13BrOS): theoretical value C, 56.08；H,4.08；Br,24.87；O,4.98；S, 9.98；Test value: C, 56.06；H,4.09；Br,24.90；O,4.96；S,9.99.ESI-MS(m/z)(M+): theoretical value is 319.99 measured value 320.14.
(2) 0.05mol raw material B1,0.06mol intermediate S1-1 is added under nitrogen protection in the there-necked flask of 500mL, uses Mixed solvent dissolves (180ml toluene, 90ml ethyl alcohol), and 0.15mol Na is then added2CO3Aqueous solution (2M) leads to nitrogen gas stirring 1 Hour, 0.0005mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, fully reacting.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate S2-1, HPLC purity 99.3%, yield 66.8%.
Elemental analysis structure (molecular formula C21H18O2S): theoretical value C, 75.42；H,5.43；O,9.57；S,9.59；Test Value: C, 75.44；H,5.41；O,9.59；S,9.56.ESI-MS(m/z)(M+): theoretical value 334.10, measured value are 334.42。
(3) intermediate 0.03mol intermediate S2-1 and 0.036mol pairs is added under nitrogen protection in the there-necked flask of 250mL Toluenesulfonic acid is dissolved with 100ml toluene, is heated to 100 DEG C, is reacted 15 hours；Contact plate is sampled, display is surplus without intermediate S2-1 It is remaining, fully reacting；After reaction, saturated sodium carbonate solution is added into reaction system to be quenched, is extracted with ethyl acetate, point Liquid, vacuum rotary steam to no fraction, gained crude product crosses neutral silica gel column, obtains intermediate after organic phase anhydrous sodium sulfate drying S3-1, HPLC purity 99.0%, yield 64.1%.
Elemental analysis structure (molecular formula C21H16OS): theoretical value C, 79.71；H,5.10；O,5.06；S,10.13；Test Value: C, 79.73；H,5.13；O,5.03；S,10.11.ESI-MS(m/z)(M+): theoretical value 316.09, measured value are 316.34。
(4) 0.15mol intermediate S3-1,30ml acetic acid are added in the there-necked flask of 100mL, 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；Contact plate is sampled, display is remaining without intermediate S3-1, fully reacting；After reaction, it is molten that sodium carbonate is added into reaction solution Liquid neutralizes, and is extracted with dichloromethane, and is layered, and takes organic phase, dry filter, and filtrate decompression rotates to no fraction, crosses silicagel column, obtain To intermediate S4-1, HPLC purity 98.6%, yield 61.3%.
Elemental analysis structure (molecular formula C21H15BrOS): theoretical value C, 63.80；H,3.82；Br,20.21；O,4.05；S, 8.11；Test value: C, 63.81；H,3.81；Br,20.22；O,4.04；S,8.12.ESI-MS(m/z)(M+): theoretical value is 394.00 measured value 394.21.
(5) 0.08mol intermediate S4-1,40ml tetrahydro furan is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml It mutters and dissolves completely, be cooled to -78 DEG C, the tetrahydrofuran that the 1.6mol/L n-BuLi of 60mL is then added into reaction system is molten Liquid is added 0.096mol triisopropyl borate ester after reacting 3h at -78 DEG C, reacts 2h, reaction system is then risen to 0 DEG C, is added Entering the 2mol/L hydrochloric acid solution of 50mL, stirs 3h, ether extraction is added in fully reacting, and anhydrous magnesium sulfate drying is added in extract liquor, Revolving, is recrystallized with alcohol solvent, obtains intermediate O1, purity 99.2%, yield 57.3%.
Elemental analysis structure (molecular formula C21H17BO3S): theoretical value C, 70.02；H,4.76；B,3.00；O,13.32；S, 8.90；Test value: C, 70.03；H,4.74；B,3.01；O,13.31；S,8.91.ESI-MS(m/z)(M+): theoretical value is 360.10 measured value 360.32.
The synthesis of intermediate II -1 is divided into five steps: raw material A bromination forms intermediate S1；In intermediate S1 and raw material B synthesis Mesosome S2；Intermediate S2 forms intermediate S3 through annulation；Intermediate S3 bromination forms intermediate S4；Finally by intermediate S4 With triisopropyl borate ester synthetic intermediate II-1, specific structure is as shown in table 2.
Table 2
B2: (the X of intermediate II -23For sulphur atom) synthesis:
(1) it weighs raw material C to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；It weighs bromine to be dissolved in glacial acetic acid, and slowly It is added dropwise in the acetic acid solution of raw material C, 5h is stirred at room temperature, sample contact plate, display is remaining without raw material C, fully reacting；Reaction terminates Afterwards, lye is added into reaction solution to neutralize, is extracted with dichloromethane, be layered, organic phase is taken to filter, filtrate decompression, which is rotated to nothing, to be evaporated Point, silicagel column is crossed, intermediate S5 is obtained；The molar ratio of the raw material C and bromine is 1:1~1.5；
(2) intermediate S5 and raw material D are weighed, is dissolved with the toluene alcohol mixed solvent that volume ratio is 1.5~3.0:1；Again Na is added2CO3Aqueous solution, Pd (PPh3)4；Under an inert atmosphere, above-mentioned mixed solution is stirred to react 10 at 95~100 DEG C It~24 hours, then cools to room temperature, filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate S10；The raw material The molar ratio of D and intermediate S5 is 1:1.5~3.0；Pd(PPh3)4Molar ratio with raw material D is 0.006~0.02:1, Na2CO3 Molar 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, is heated to 140~150 DEG C, reaction 8~12 hours；Contact plate is sampled, display is remaining without intermediate S6, fully reacting；Reaction system is cooled to room temperature, saturation is added Sodium chloride solution, be extracted with ethyl acetate, liquid separation, organic phase is dry with anhydrous sodium sulfate, vacuum rotary steam, gained crude product mistake Neutral silica gel column obtains intermediate S7；The intermediate S6 is 1:1~1.5 with the molar ratio to cesium carbonate；
(4) it weighs intermediate S7 to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；It weighs bromine to be dissolved in glacial acetic acid, and delays Slowly it is added dropwise in the acetic acid solution of intermediate S7,5h is stirred at room temperature, sample contact plate, display is remaining without intermediate S7, fully reacting； After reaction, lye is added into reaction solution to neutralize, is extracted with dichloromethane, be layered, organic phase is taken to filter, filtrate decompression rotation It steams to no fraction, crosses silicagel column, obtain intermediate S8；The molar ratio of the intermediate S7 and bromine is 1:1~1.5；
(5) under nitrogen protection, it weighs intermediate S8 to be dissolved in tetrahydrofuran, is cooled to -78 DEG C, then to reaction system The middle tetrahydrofuran solution that 1.6mol/L n-BuLi is added, is added triisopropyl borate ester after reacting 3h at -78 DEG C, reacts Then reaction system is risen to 0 DEG C by 2h, 2mol/L hydrochloric acid solution is added, and stirs 3h, and ether extraction, extraction is added in fully reacting Anhydrous magnesium sulfate drying is added in liquid, and revolving is recrystallized with alcohol solvent, obtains intermediate II -2；The intermediate S8 and positive fourth The molar ratio of base lithium is 1:1~1.5；The molar ratio of the intermediate S8 and triisopropyl borate ester is 1:1~1.5.
The synthesis of intermediate II -2 is divided into five steps: raw material C bromination forms intermediate S5；In intermediate S5 and raw material D synthesis Mesosome S6；Intermediate S6 forms intermediate S7 through annulation；Intermediate S7 bromination forms intermediate S8；Finally by intermediate S8 With triisopropyl borate ester synthetic intermediate II-2, specific structure is as shown in table 3.
Table 3
B3. (the X of intermediate II -33For C1-10The alkylidene that the alkylidene or aryl that linear or branched alkyl group replaces replace) Synthesis
(1) raw material E and raw material F are weighed, is dissolved with the toluene alcohol mixed solvent that volume ratio is 1.5~3.0:1；It adds Na2CO3Aqueous solution, Pd (PPh3)4；Under nitrogen protection, above-mentioned mixed solution is stirred to react 10~24 at 95~100 DEG C Hour, it then cools to room temperature, filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate S9；The raw material F and original The molar ratio for expecting E is 1:1.5~3.0；Pd(PPh3)4Molar ratio with raw material F is 0.006~0.02:1, Na2CO3With raw material F Molar ratio be 2.0~3.0:1；
(2) under nitrogen protection, intermediate S9 is weighed, with tetrahydrofuran stirring and dissolving；Mixed solution is dropped with ice salt bath The tetrahydrofuran solution of the correspondence grignard reagent of brand-new is slowly added dropwise to 0 DEG C in temperature, reacts at room temperature 6~12 hours, samples contact plate, Display is remaining without intermediate S10, fully reacting；Naturally it places to room temperature, filtering, filtrate carries out vacuum rotary steam to no fraction, mistake Neutral silica gel column obtains intermediate S10；The molar ratio of the intermediate S9 and grignard reagent is 1:2~4；
(3) under nitrogen protection, intermediate S10 is weighed, is the dense H of 1:2.0~4.0 with volume ratio3PO4With the mixing of water Liquid reacts at room temperature 6~12 hours as solvent, dissolution, samples contact plate, display is remaining without intermediate S2, fully reacting；It is added NaOH aqueous solution is neutralized to pH=7, and methylene chloride extraction is added, and layering takes organic phase to filter, and filtrate decompression, which is rotated to nothing, to be evaporated Point, neutral silica gel column is crossed, intermediate S11 is obtained；The molar ratio of the intermediate S10 and concentrated phosphoric acid is 1:3~6；
(4) it weighs intermediate S11 to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and It is slowly added dropwise into the acetic acid solution of intermediate S11,5h is stirred at room temperature, sample contact plate, display is remaining without intermediate S11, reaction Completely；After reaction, lye is added into reaction solution to neutralize, is extracted with dichloromethane, be layered, take organic phase to filter, filtrate Vacuum rotary steam crosses silicagel column, obtains intermediate S12 to no fraction；The molar ratio of the intermediate S11 and bromine be 1:1~ 1.5；
(5) under nitrogen protection, it weighs intermediate S12 to be dissolved in tetrahydrofuran, is cooled to -78 DEG C, then to reactant The tetrahydrofuran solution of 1.6mol/L n-BuLi is added in system, triisopropyl borate ester is added after reacting 3h at -78 DEG C, reacts Then reaction system is risen to 0 DEG C by 2h, 2mol/L hydrochloric acid solution is added, and stirs 3h, and ether extraction, extraction is added in fully reacting Anhydrous magnesium sulfate drying is added in liquid, and revolving is recrystallized with alcohol solvent, obtains intermediate II -3；The intermediate S12 and positive fourth The molar ratio of base lithium is 1:1~1.5；The molar ratio of the intermediate S12 and triisopropyl borate ester is 1:1~1.5.
The synthesis of intermediate II -3 is divided into five steps: by raw material E and raw material F synthetic intermediate S9；Intermediate S9 and format examination Agent generates intermediate S10；Intermediate S10 cyclization generates intermediate S11；Intermediate S11 bromination forms intermediate S12；Finally by Intermediate S12 and triisopropyl borate ester synthetic intermediate II-3, specific structure are as shown in table 4.
Table 4
B4: (the X of intermediate II -43For aryl replace tertiary amine groups) synthesis
(1) raw material G and raw material H are weighed, is dissolved with the toluene alcohol mixed solvent that volume ratio is 1.5~3.0:1；It adds Na2CO3Aqueous solution, Pd (PPh3)4；Under nitrogen protection, above-mentioned mixed solution is stirred to react 10~24 at 95~100 DEG C Hour, it then cools to room temperature, filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate S13；The raw material H with The molar ratio of raw material G is 1:1.5~3.0；Pd(PPh3)4Molar ratio with raw material H is 0.006~0.02:1, Na2CO3With raw material The molar ratio of H is 2.0~3.0:1；
(2) under nitrogen protection, intermediate S13 prepared by previous step is dissolved in o-dichlorohenzene, triphenylphosphine is added, It is stirred to react at 170~190 DEG C 12~16 hours, is cooled to room temperature after reaction, filter, filtrate decompression revolving is excessively neutral Silicagel column obtains intermediate S14；The intermediate S13 and triphenylphosphine molar ratio are 1:1~2；
(3) under nitrogen protection, intermediate S14, raw material J, sodium tert-butoxide, Pd are successively weighed2(dba)3, tri-tert-butylphosphine, It is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, samples contact plate, display is surplus without intermediate S14 It is remaining, fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate S15；The molar ratio of the intermediate S14 and raw material J is 1:1~2；The Pd2(dba)3Molar ratio with intermediate S14 is The molar ratio of 0.006~0.02:1, the tri-tert-butylphosphine and intermediate S14 are 0.006~0.02:1；The sodium tert-butoxide with The molar ratio of intermediate S14 is 2.0~3.0:1；
(4) it weighs intermediate S15 to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and It is slowly added dropwise into the acetic acid solution of intermediate S15,5h is stirred at room temperature, sample contact plate, display is remaining without intermediate S15, reaction Completely；After reaction, lye is added into reaction solution to neutralize, is extracted with dichloromethane, be layered, take organic phase to filter, filtrate Vacuum rotary steam crosses silicagel column, obtains intermediate S16 to no fraction；The molar ratio of the intermediate S15 and bromine be 1:1~ 1.5；
(5) under nitrogen protection, it weighs intermediate S16 to be dissolved in tetrahydrofuran, is cooled to -78 DEG C, then to reactant The tetrahydrofuran solution of 1.6mol/L n-BuLi is added in system, triisopropyl borate ester is added after reacting 3h at -78 DEG C, reacts Then reaction system is risen to 0 DEG C by 2h, 2mol/L hydrochloric acid solution is added, and stirs 3h, and ether extraction, extraction is added in fully reacting Anhydrous magnesium sulfate drying is added in liquid, and revolving is recrystallized with alcohol solvent, obtains intermediate II -4；The intermediate S16 and positive fourth The molar ratio of base lithium is 1:1~1.5；The molar ratio of the intermediate S16 and triisopropyl borate ester is 1:1~1.5.
The synthesis of intermediate II -4 is divided into five steps: by raw material G and raw material H synthetic intermediate S13；Intermediate S13 is through cyclization Reaction forms intermediate S14；Intermediate S14 and raw material J synthetic intermediate S15；Intermediate S15 bromination forms intermediate S16；Most Afterwards by intermediate S16 and triisopropyl borate ester synthetic intermediate II-4, specific structure is as shown in table 5.
Table 5
Embodiment 2: the synthesis of compound 5:
0.01mol intermediate M1,0.015mol raw material Q1 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL, (90ml toluene, 45ml ethyl alcohol) is dissolved with mixed solvent, 0.03mol Na is then added2CO3Aqueous solution (2M) leads to nitrogen gas stirring 1 Hour, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, fully reacting.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, purity 99.1%, yield 79.9%.Elemental analysis structure (molecular formula C50H32O2): theoretical value C, 90.33；H,4.85；O,4.81；Test value: C, 90.35；H,4.83；O,4.82.ESI-MS(m/z) (M+): theoretical value 664.24, measured value 664.49.
Embodiment 3: the synthesis of compound 14:
0.01mol intermediate M1,0.015mol raw material Q2 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml, (90ml toluene, 45ml ethyl alcohol) is dissolved with mixed solvent, 0.03mol Na is then added2CO3Aqueous solution (2M) leads to nitrogen gas stirring 1 Hour, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, fully reacting.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, purity 98.9%, yield 77.8%.Elemental analysis structure (molecular formula C40H28OS): theoretical value C, 86.30；H,5.07；O,2.87；S,5.76；Test value: C, 86.32；H,5.05；O,2.85；S, 5.78。ESI-MS(m/z)(M+): theoretical value 556.19, measured value 556.55.
Embodiment 4: the synthesis of compound 24:
0.01mol intermediate M2,0.015mol raw material O1 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml, (90ml toluene, 45ml ethyl alcohol) is dissolved with mixed solvent, 0.03mol Na is then added2CO3Aqueous solution (2M) leads to nitrogen gas stirring 1 Hour, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, fully reacting.Natural cooling, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, purity 99.1%, yield 78.1%.Elemental 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, measured value 632.48.
Embodiment 5: the synthesis of compound 34:
The preparation method of compound 34 is with embodiment 2, the difference is that using intermediate M3 replacement intermediate M1 in Mesosome Q3 replaces intermediate Q1.Elemental analysis structure (molecular formula C52H44): theoretical value C, 93.37；H,6.63；Test value: C, 93.36；H,6.64.ESI-MS(m/z)(M+): theoretical value 668.34, measured value 668.61.
Embodiment 6: the synthesis of compound 42:
The preparation method of compound 42 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate Q4.Element Analyze structure (molecular formula C46H33NO): theoretical value C, 89.73；H,5.40；N,2.27；O,2.60；Test value: C, 89.71；H, 5.42；N,2.25；O,2.62.ESI-MS(m/z)(M+): theoretical value 615.26, measured value 615.52.
Embodiment 7: the synthesis of compound 56:
The preparation method of compound 56 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate R1.Element Analyze structure (molecular formula C46H33NS): theoretical value C, 86.44；H,4.74；N,4.11；S,4.71；Test value: C, 86.44；H, 4.74；N,4.11；S,4.71.ESI-MS(m/z)(M+): theoretical value 680.23, measured value 680.45.
Embodiment 8: the synthesis of compound 62:
The preparation method of compound 62 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate O2.Element Analyze 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,2.25；O,2.62.ESI-MS(m/z)(M+): theoretical value 615.26, measured value 615.43.
Embodiment 9: the synthesis of compound 65:
The preparation method of compound 65 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate O3.Element Analyze structure (molecular formula C46H33NO): theoretical value C, 89.73；H,5.40；N,2.27；O,2.60；Test value: C, 89.74；H, 5.41；N,2.24；O,2.61.ESI-MS(m/z)(M+): theoretical value 615.26, measured value 615.49.
Embodiment 10: the synthesis of compound 74:
The preparation method of compound 74 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate Q5.Element Analyze structure (molecular formula C49H39N): theoretical value C, 91.69；H,6.12；N,2.18；Test value: C, 91.67；H,6.15；N, 2.18。ESI-MS(m/z)(M+): theoretical value 641.31, measured value 641.64.
Embodiment 11: the synthesis of compound 77:
The preparation method of compound 77 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate Q6.Element Analyze 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 641.57.
Embodiment 12: the synthesis of compound 83:
The preparation method of compound 83 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate R2.Element Analyze structure (molecular formula C52H38N2): theoretical value C, 90.40；H,5.54；N,4.05；Test value: C, 90.42；H,5.52；N, 4.06。ESI-MS(m/z)(M+): theoretical value 690.30, measured value 690.64.
Embodiment 13: the synthesis of compound 86:
The preparation method of compound 86 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate R3.Element Analyze structure (molecular formula C52H38N2): theoretical value C, 90.40；H,5.54；N,4.05；Test value: C, 90.43；H,5.53；N, 4.04。ESI-MS(m/z)(M+): theoretical value 690.30, measured value 690.59.
Embodiment 14: the synthesis of compound 89:
The preparation method of compound 89 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate O4.Element Analyze structure (molecular formula C52H37NO): theoretical value C, 90.27；H,5.39；N,2.02；O,2.31；Test value: C, 90.26；H, 5.38；N,2.03；O,2.33.ESI-MS(m/z)(M+): theoretical value 691.29, measured value 691.52.
Embodiment 15: the synthesis of compound 95:
The preparation method of compound 95 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate O5.Element Analyze structure (molecular formula C52H37NO): theoretical value C, 90.27；H,5.39；N,2.02；O,2.31；Test value: C, 90.28；H, 5.38；N,2.00；O,2.34.ESI-MS(m/z)(M+): theoretical value 691.29, measured value 691.55.
Embodiment 16: the synthesis of compound 100:
The preparation method of compound 100 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate P1.Member Element analysis structure (molecular formula C52H37NS): theoretical value C, 88.22；H,5.27；N,1.98；S,4.53；Test value: C, 88.24； H,5.25；N,1.97；S,4.54.ESI-MS(m/z)(M+): theoretical value 707.26, measured value 707.51.
Embodiment 17: the synthesis of compound 106:
The preparation method of compound 106 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate Q7.Member Element analysis 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 717.62.
Embodiment 18: the synthesis of compound 115:
The preparation method of compound 115 is with embodiment 2, the difference is that using intermediate M4 replacement intermediate M1 in Mesosome P2 replaces intermediate Q1.Elemental analysis structure (molecular formula C47H30N4S): theoretical value C, 82.67；H,4.43；N,8.21；S, 4.70；Test value: C, 82.65；H,4.42；N,8.23；S,4.70.ESI-MS(m/z)(M+): theoretical value 682.22, actual measurement Value is 682.52.
Embodiment 19: the synthesis of compound 121:
The preparation method of compound 121 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate O6.Member Element analysis structure (molecular formula C56H37NO): theoretical value C, 90.90；H,5.04；N,1.89；O,2.16；Test value: C, 90.92； H,5.05；N,1.88；O,2.15.ESI-MS(m/z)(M+): theoretical value 739.29, measured value 739.57.
Embodiment 20: the synthesis of compound 135:
The preparation method of compound 135 is with embodiment 2, the difference is that replacing intermediate Q1 using intermediate Q8.Member Element analysis structure (molecular formula C59H43N): theoretical value C, 92.51；H,5.66；N,1.83；Test value: C, 92.52；H,5.67；N, 1.81。ESI-MS(m/z)(M+): theoretical value 765.34, measured value 765.66.
Organic compound of the invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as Luminescent layer Subjective and Objective materials'use.To the compounds of this invention 5,14,24,34,42,56,62,65,74,77,83,86,89,95, 100,106,121,135 respectively carry out T1 energy level, hot property, HOMO energy level test, the results are shown in Table 6.
Table 6
Compound T1(ev) Tg(℃) Td(℃) HOMO energy level (ev) Functional layer
Compound 5 2.74 142 412 -5.75 Luminescent layer
Compound 14 2.75 131 399 -5.85 Luminescent layer
Compound 24 2.77 136 407 -5.87 Luminescent layer
Compound 34 2.74 141 410 -5.76 Luminescent layer
Compound 42 2.78 135 406 -5.61 Electronic barrier layer
Compound 56 2.76 143 415 -5.68 Electronic barrier layer
Compound 62 2.76 137 407 -5.69 Electronic barrier layer
Compound 65 2.74 135 404 -5.66 Electronic barrier layer
Compound 74 2.73 138 411 -5.65 Electronic barrier layer
Compound 77 2.74 137 413 -5.64 Electronic barrier layer
Compound 83 2.75 142 415 -5.68 Electronic barrier layer
Compound 86 2.76 144 417 -5.66 Electronic barrier layer
Compound 89 2.76 143 414 -5.69 Electronic barrier layer
Compound 95 2.74 145 416 -5.66 Electronic barrier layer
Compound 100 2.75 147 418 -5.68 Electronic barrier layer
Compound 106 2.74 148 420 -5.67 Electronic barrier layer
Compound 121 2.78 151 422 -5.77 Luminescent layer
Compound 135 2.77 155 428 -5.75 Luminescent layer
Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of 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 company DSC204F1 differential scanning calorimeter) Measurement, 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 analyzer on be measured, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy level be by Ionizing energy test macro (IPS3) test, is tested as atmospheric environment.
By upper table data it is found that organic compound of the invention has different HOMO energy levels, different function can be applied to Ergosphere, the present invention is using fluorenes as the organic compound of core triplet with higher and higher thermal stability, so that institute The OLED device efficiency containing organic compound of the present invention and service life of production get a promotion.
Below by way of device embodiments 1~18 and device comparative example 1 OLED material that the present invention will be described in detail synthesizes in device Application effect in part.Device embodiments 2~18 of the present invention, the device compared with device embodiments 1 of device comparative example 1 Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material is also kept Unanimously, except that device embodiments 2~12 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 13~18 pairs of devices of example converts.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, preparation step includes: a) to clean transparent substrate Ito anode layer 2 on layer 1, is cleaned each 15 minutes respectively with deionized water, acetone, EtOH Sonicate, then in plasma clean It is 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 as hole injection layer 3；C) on hole injection layer 3, hole mobile material is deposited by vacuum evaporation mode NPB, with a thickness of 60nm, which is hole transmission layer 4；D) on hole transmission layer 4, electronics resistance is deposited by vacuum evaporation mode Barrier material the compounds of this invention 42, with a thickness of 20nm, which is electronic barrier layer 5；E) hair is deposited on electronic barrier layer 5 Photosphere 6 uses CBP as material of main part, Ir (ppy)3As dopant material, Ir (ppy)3Mass ratio with CBP is 10:90, thick Degree is 30nm；F) on luminescent layer 6, electron transport material TPBI is deposited by vacuum evaporation mode, with a thickness of 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, with a thickness of 1nm, which is electron injecting layer 8；H) on electron injecting layer 8, vacuum evaporation cathode Al (100nm), the layer are cathode reflection electrode layer 9.The molecular structural formula of associated materials is as follows:
Device embodiments 2: the electronic blocking layer material of electroluminescent device is the compounds of this invention 56.Device embodiments 3: The electronic blocking layer material of electroluminescent device is the compounds of this invention 62.Device embodiments 4: the electronics resistance of electroluminescent device Barrier material is the compounds of this invention 65.Device embodiments 5: the electronic blocking layer material of electroluminescent device is chemical combination of the present invention Object 74.Device embodiments 6: the electronic blocking layer material of electroluminescent device is the compounds of this invention 77.Device embodiments 7: electricity The electronic blocking layer material of electroluminescence device is the compounds of this invention 83.Device embodiments 8: the electronic blocking of electroluminescent device Layer material is the compounds of this invention 86.Device embodiments 9: the electronic blocking layer material of electroluminescent device is the compounds of this invention 89.Device embodiments 10: the electronic blocking layer material of electroluminescent device is the compounds of this invention 95.Device embodiments 11: electricity The electronic blocking layer material of electroluminescence device is the compounds of this invention 100.Device embodiments 12: the electronics resistance of electroluminescent device Barrier material is the compounds of this invention 106.Device embodiments 13: the electronic blocking layer material of electroluminescent device is NPB, electroluminescent The luminescent layer material of main part of luminescent device becomes the compounds of this invention 5, and dopant material is Ir (ppy)3, Ir (ppy)3With compound 5 Mass ratio be 10:90.Device embodiments 14: the electronic blocking layer material of electroluminescent device is NPB, electroluminescent device Luminescent layer material of main part becomes the compounds of this invention 34, and dopant material is Ir (ppy)3, Ir (ppy)3With the mass ratio of compound 34 For 10:90.Device embodiments 15: the electronic blocking layer material of electroluminescent device is NPB, the luminescent layer master of electroluminescent device Body material becomes the compounds of this invention 121, and dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 121 is 10: 90.Device embodiments 16: the electronic blocking layer material of electroluminescent device is NPB, the luminous layer main body material of electroluminescent device Material becomes the compounds of this invention 135, and dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 135 is 10:90.Device Part embodiment 17: the electronic blocking layer material of electroluminescent device is NPB, and the luminescent layer material of main part of electroluminescent device becomes The compounds of this invention 14 and compound GHN, dopant material are Ir (ppy)3, compound 14, GHN and Ir (ppy)3Three's mass ratio For for 60:30:10.Device embodiments 18: the electronic blocking layer material of electroluminescent device is NPB, the hair of electroluminescent device Photosphere material of main part becomes the compounds of this invention 24 and compound GHN, and dopant material is Ir (ppy)3, compound 24, GHN and Ir (ppy)3Three's mass ratio is 60:30:10.Device comparative example 1: the electronic blocking layer material of electroluminescent device is NPB, electricity The luminescent layer material of main part of electroluminescence device is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3With the matter of CBP Amount is than being 10:90.
After the production of above-mentioned electroluminescent device, the current efficiency of measurement device and service life, the result is shown in shown in table 7.
Table 7
Note: life-span test system is owner of the present invention and the OLED device life test that Shanghai University is studied jointly Instrument.
Can be seen that by the result of table 7 of the present invention can be applied to OLED luminescent device by the machine compound of core of fluorenes Production, and compared with device comparative example 1, either efficiency or service life obtain larger change than known OLED material, special It is not the biggish promotion of life time decay acquisition of device.
The OLED device of further material preparation of the present invention is able to maintain the long-life at high temperature, by device embodiments 1~18 and device comparative example 1 in 85 DEG C of progress high temperature driven life tests, acquired results are as shown in table 8.
Table 8
From the data of table 8 it is found that device embodiments 1~18 are the device architecture of material of the present invention and known materials collocation, It is compared with device comparative example 1, under high temperature, OLED device provided by the invention has the driving service life well.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of using fluorenes as the organic compound of core, which is characterized in that the structure of the organic compound such as general formula (1) institute Show:
In general formula (1), Ar is expressed as phenyl, dibiphenylyl, terphenyl, naphthalene, anthryl, phenanthryl, pyrenyl, furyl, thiophene One of base, pyridyl group, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical；
In general formula (1), R is expressed as structure shown in general formula (2)；
In general formula (2), X1、X2、X3Independently be expressed as oxygen atom, sulphur atom, C1-10The Asia that linear or branched alkyl group replaces One of the tertiary amine groups that alkyl, the alkylidene of aryl substitution, alkyl or aryl replace；
In general formula (2),Pass through CL1-CL2Key, CL2-CL3Key or CL3-CL4Key withConnection.
2. organic compound according to claim 1, which is characterized in that the general formula (2) indicates are as follows:
Any one.
3. organic compound according to claim 1, which is characterized in that the concrete structure formula of the organic compound are as follows:
In any one.
4. a kind of preparation method of any one of claims 1 to 3 organic compound, which is characterized in that sent out in preparation process Raw reaction equation are as follows:
Specifically the preparation method comprises the following steps: weighing intermediate compound I and intermediate II, the toluene alcohol mixed solvent for being 1.5~3:1 with volume ratio Dissolution；Add Na2CO3Aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature It is reacted 10~24 hours at 90~110 DEG C of degree, cooling, filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；
The molar ratio of the intermediate compound I and intermediate II is 1:1.0~1.5；Pd(PPh3)4Molar ratio with intermediate compound I is 0.006~0.02:1, Na2CO3Molar ratio with intermediate compound I is 2.0~3.0:1.
5. one kind is as claimed in any one of claims 1 to 3 to be used to prepare organic electroluminescence hair by the organic compound of core of fluorenes Optical device.
6. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer It is described in any item using fluorenes as the organic compound of core containing claims 1 to 3.
7. a kind of organic electroluminescence device, including electronic barrier layer, which is characterized in that the electronic blocking layer material is right It is required that 1~3 is described in any item using fluorenes as the organic compound of core.
8. a kind of organic electroluminescence device, including luminescent layer, which is characterized in that the luminescent layer, which contains claims 1 to 3, appoints Using fluorenes as the organic compound of core described in one.
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Patentee after: Jiangsu March Technology Co., Ltd

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Patentee before: VALIANT Co.,Ltd.