CN107573356A - A kind of fluorenes class organic compound and its application in OLED - Google Patents
A kind of fluorenes class organic compound and its application in OLED Download PDFInfo
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- 0 C1*c2ccccc2*C1 Chemical compound C1*c2ccccc2*C1 0.000 description 9
- LYBKGVDKODVUPQ-UHFFFAOYSA-N CC(C)(C1C=CC(NC2C=CC=CC2C(OC)=O)=CC1C1(C)C)c2c1cccc2 Chemical compound CC(C)(C1C=CC(NC2C=CC=CC2C(OC)=O)=CC1C1(C)C)c2c1cccc2 LYBKGVDKODVUPQ-UHFFFAOYSA-N 0.000 description 1
- SISQKQNJHCDULL-UHFFFAOYSA-N COC(c1ccccc1)=N Chemical compound COC(c1ccccc1)=N SISQKQNJHCDULL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of fluorenes class organic compound and its application in OLED, the structure of the compound is that fluorenes is connected by carbon-carbon bond with benzo hexatomic ring and six-membered 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, has higher triplet (T1)；And steric hindrance is big, it is not easy 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, after the compounds of this invention is applied to OLED, the luminous efficiency and service life of device can effectively be lifted.
Description
Technical field
The present invention relates to technical field of semiconductors, has fluorenes class machine compound and its answering on OLED more particularly, to a kind of
With.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used for make
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 compound in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are applied in fields such as smart mobile phone, tablet personal computers, further will also be to electricity
Depending on etc. large scale application field extension, still, with reality products application requirement compare, the luminous efficiency of OLED and use
The performances such as life-span also need to further be lifted.Proposing high performance research to OLED luminescent devices at present includes：Reduce the drive of device
Dynamic voltage, the luminous efficiency for improving device, service life of raising device etc..In order to realize constantly carrying for the performance of OLED
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 various organic functional materials possess good photoelectric properties,
For example, as charge transport materials, it is desirable to there is 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..
The oled light sulfate ferroelectric functional material film layer for forming OLED comprises at least more than two layers structure, is applied in 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 injects 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, 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, the difference in functionality film layer of the industry application requirement for current OLED and 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, 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.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of fluorenes class organic compound and its organic
Application on electroluminescent device.The compounds of this invention has higher glass transition temperature and molecule heat endurance, suitably
HOMO and lumo energy, higher Eg, are optimized by device architecture, can effectively lift the photoelectric properties and OLED devices of OLED
The life-span of part.Technical scheme is as follows：
A kind of fluorenes class organic compound, shown in the structure such as formula (1) of the organic compound：
In formula (1), Ar1It is expressed as substituted or unsubstituted C6-60Aryl, containing one or more heteroatomic substitutions or
Unsubstituted 5~60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；
Ar2It is expressed as singly-bound, substituted or unsubstituted C6-60Arlydene, containing one or more heteroatomic substitutions or not
5~60 yuan of heteroarylidenes of substitution；The hetero atom is nitrogen, oxygen or sulphur；
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 imido grpup of the alkylidene in generation, alkyl-substituted imido grpup or aryl substitution；
Ar3It is expressed as substituted or unsubstituted C6-60Aryl, contain one or more heteroatomic substituted or unsubstituted 5-
60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；
In formula (2), R1It is expressed as structure shown in formula (3)；
In formula (3), X1、X2Be expressed as oxygen atom, sulphur atom, C1-10 straight or branched alkyls independently substitutes
One kind in alkylidene, the alkylidene of aryl substitution, alkyl-substituted imido grpup or the imido grpup of aryl substitution；Formula (3) is logical
Cross CL1-CL2Key, CL2-CL3Key or CL3-CL4Key and formula (2) connection.
Preferably, Ar2It is expressed as phenylene, sub- dibiphenylyl, sub- terphenyl, naphthylene, anthrylene, phenanthrylene, Asia
One kind in pyrenyl, furylidene, sub- thienyl, sub- pyridine radicals, sub- pyrimidine radicals, sub- pyridazinyl, sub- pyrazinyl or sub- triazine radical,
Ar2It is also shown as singly-bound；Ar1And Ar3Independently be expressed as phenyl, dibiphenylyl, terphenyl, naphthyl, anthryl, phenanthryl,
One kind in pyrenyl, furyl, thienyl, pyridine radicals, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical.
Preferably, the compound is selected from formula (4), formula (5), formula (6) or structure shown in formula (7)：
The symbol and mark wherein used is with the implication being given above.
Preferably, the compound is selected from formula (8), formula (9), formula (10) or structure shown in formula (11)：
The symbol and mark wherein used is with the implication being given above.
Preferably, the compound is selected from formula (12), formula (13), formula (14) or structure shown in formula (15)：
The implication that the symbol and mark tool wherein used is given above.
Preferably, the compound is selected from formula (16), formula (17), formula (18) or structure shown in formula (19)：
The implication that the symbol and mark tool wherein used is given above.
It is furthermore preferred that the formula (2) is expressed as：
Any one.More preferably
, the concrete structure formula of the fluorenes class organic compound is：
In any one.
The applicant additionally provides the preparation method of the fluorenes class organic compound, the reactional equation occurred in preparation process
Formula is：
Specifically preparation method is：Intermediate M1 and intermediate M2 are weighed, is 1.5~3 with volume ratio:1 toluene ethanol mixes
Bonding solvent dissolves；Add Na2CO3The aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in
Reacted 10~24 hours at 90~110 DEG C of reaction temperature, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain mesh
Mark product；
The intermediate M1 and intermediate M2 mol ratio is 1:1.0~1.5；Pd(PPh3)4With intermediate M1 mol ratio
For 0.006~0.02:1, Na2CO3Mol ratio with intermediate M1 is 2.0~3.0:1.
The applicant additionally provides a kind of described fluorenes class organic compound and is used to prepare answering for organic electroluminescence device
With.The organic electroluminescence device includes at least one layer of functional layer and contains described fluorenes class organic compound.
The applicant additionally provides a kind of organic electroluminescence device, including electronic barrier layer, the electronic barrier layer material
Expect for described fluorenes class organic compound.The applicant additionally provides a kind of organic electroluminescence device, including luminescent layer, described
Luminescent layer contains described fluorenes class organic compound.
The present invention is beneficial to be had technical effect that：
The compounds of this invention is connected using fluorenes as skeleton with benzo hexatomic ring and six-membered ring structure with carbon-carbon bond, carbon-carbon bond
Connection had both improved stability of material, and to turn avoid the active position of branched group exposed；Such compound is larger except fluorenes has
Rigidly 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
The stereochemical structure of the compounds of this invention material is more stable.And the compounds of this invention triplet T1 is mainly distributed on side chain
On, side chain has high T1 energy levels, therefore the compounds of this invention equally has high T1 energy levels；The compounds of this invention is as OLED's
During electronic barrier layer materials'use, high T1 energy levels can effectively stop energy from luminescent layer to hole transmission layer transmission, reduce
Energy loss, makes luminescent layer material of main part energy be sufficiently transmitted to dopant material, so as to lift materials application after device
Luminous efficiency.
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；During light emitting functional layer materials'use as OLED luminescent devices, fluorenes collocation
Side chain in the scope of the invention can effectively improve exciton utilization rate and high fluorescent radiation efficiency, reduce the efficiency under 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 in OLED application
When, optimized by device architecture, high membranous layer stability can be kept, can effectively lift the photoelectric properties and OLED of OLED
In the life-span of device, there is good application effect and industrialization 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.
Fig. 2 is the curve that the compounds of this invention luminous efficiency varies with temperature.
Embodiment
Embodiment 1：Intermediate M1 and intermediate M2 synthesis
A. intermediate M1 synthesis：
(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, 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, a large amount of white precipitates is generated, is subsequently cooled to room temperature, add
Enter saturation NHCl4Form salt is converted into alcohol；After completion of the reaction, ether extracts, and dries revolving, crosses silicagel column, obtains slightly yellow
The solid tertiary alcohol intermediates W of color；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, reaction terminate rear liquid separation, and aqueous phase is extracted with toluene, and organic phase uses anhydrous sodium sulfate after merging
Dry, filter, filter cake use ethyl acetate rinse again, and filtrate and flushing liquor are rotated to solvent-free, mistake silicagel column, obtain intermediate
X.The volume of the 48%HBr aqueous solution is 20ml corresponding per 0.01mol intermediates W.
(4) under nitrogen protection, weigh intermediate X 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, reacted
2h, reaction system is then risen to 0 DEG C, add 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, adds ether extraction, extraction
Liquid adds anhydrous magnesium sulfate and dried, and revolving, is recrystallized with alcohol solvent, obtains intermediate Y；The intermediate X and n-BuLi
Mol ratio be 1:1~1.5；The intermediate X and the mol ratio of triisopropyl borate ester are 1:1~1.5.
(5) intermediate Y and raw material E 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 90~110 DEG C of reaction temperature
Lower reaction 10~24 hours, cooling, filtering reacting solution, filtrate revolving, silicagel column is crossed, obtains target product M1；The centre
Body Y and raw material E mol ratio is 1:1.0~1.5；Pd(PPh3)4Mol ratio with intermediate Y is 0.006~0.02:1,
Na2CO3Mol ratio with intermediate Y is 2.0~3.0:1.
By taking intermediate M1-2 synthesis as an example：
(1) 250mL there-necked flask, under the atmosphere for being passed through nitrogen, 0.05mol raw materials U1,0.06molMg powder is added, is used
60ml dry tetrahydrofurans dissolve, and add 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, stirring reaction 4 hours, no magnesium powder is remaining, and reaction is complete, generates among grignard reagent
Body V1, without purification, directly carry out in next step.
(2) 250mL there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.03mol9- Fluorenones, and 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 extracts, and dries revolving, crosses silicon
Glue post, obtain solid tertiary alcohol intermediates W1, the HPLC purity 99.2% of yellowish, yield 74.7%.
Elementary 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) 250mL there-necked flask, 0.02mol intermediate W1 are added, is dissolved with 50ml toluene, 48%HBr water is slowly added dropwise
Solution (40ml), stirring reaction 24 hours at 25 DEG C, reaction terminate rear liquid separation, and aqueous phase is extracted with toluene, after organic phase merges
With anhydrous sodium sulfate drying, filter, filter cake uses ethyl acetate rinse again, and filtrate and flushing liquor are rotated to solvent-free, mistake silica gel
Post, obtain intermediate M1-1, HPLC purity 99.4%, yield 73.5%.
Elementary 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.
(4) under nitrogen protection, weigh intermediate M1-1 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, reaction system is then risen to 0 DEG C, add 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, adds ether extraction, extraction
Liquid adds anhydrous magnesium sulfate and dried, and revolving, is recrystallized with alcohol solvent, obtains intermediate Y；The intermediate M1-1 and normal-butyl
The mol ratio of lithium is 1:1~1.5；The mol ratio of the intermediate M1-1 and triisopropyl borate ester are 1:1~1.5.
Elementary analysis structure (molecular formula C19H15BO2)：Theoretical value C, 79.76；H,5.28；B,3.78；Test value：C,
79.76；H,5.28；B,3.77.ESI-MS(m/z)(M+)：Theoretical value 286.12, measured value 286.66.
(5) intermediate Y and raw material E 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 90~110 DEG C of reaction temperature
Lower reaction 10~24 hours, cooling, filtering reacting solution, filtrate revolving, silicagel column is crossed, obtains target product M1-2；In described
Mesosome Y and raw material E mol ratio is 1:1.0~1.5；Pd(PPh3)4Mol ratio with intermediate Y is 0.006~0.02:1,
Na2CO3Mol ratio with intermediate Y is 2.0~3.0:1.
Elementary analysis structure (molecular formula C25H17Br)：Theoretical value C, 75.58；H,4.31；Br,20.11；Test value：C,
75.58；H,4.30；Br,20.12.ESI-MS(m/z)(M+)：Theoretical value 396.05, measured value 396.50.
B. intermediate M2 is R-B (OH)2Synthesis：
When X isWhen (R2For methyl or phenyl)：
(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, reaction is stirred at room temperature until reaction completely, after reaction terminates, alkali is added into reaction solution
Liquid is neutralized, and is extracted with dichloromethane, is layered, takes organic phase to filter, and filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained
To intermediate S1；In the reaction, the molar ratio of raw material A and bromine is 1:1~3；
(2) under nitrogen protection, intermediate S1, raw material B, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine,
It is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows that no intermediate S1 is remained
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
S2.In above-mentioned reaction, intermediate S1 and raw material B mol ratio is 1:1~2；The mol ratio of intermediate S1 and sodium tert-butoxide is 1:1
~3；Intermediate S1 and Pd2(dba)3Mol ratio with tri-butyl phosphine is 1:0.01~0.05；
(3) under nitrogen protection, intermediate S2 is weighed, tetrahydrofuran stirring and dissolving is added, 0 DEG C is cooled to ice salt bath；
Then the tetrahydrofuran solution of the corresponding RMgBr of brand-new is slowly added dropwise, reacts at room temperature 6~12 hours, sample point plate, display
Remaining without intermediate S2, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, crosses neutral silica gel
Post, obtain intermediate S3.In above-mentioned reaction, the mol ratio of intermediate S2 and grignard reagent kit is 1:2~4；
(4) under nitrogen protection, intermediate S3 is weighed, adds dense H3PO4It is 1 with water volume ratio:3 mixed liquor, stirring are mixed
Close, react at room temperature 6~12 hours, sample point plate, show that no intermediate S3 is remaining, reaction is complete；The NaOH aqueous solution is added to neutralize
To pH=7, dichloromethane extraction being added, layering, takes organic phase to filter, filtrate decompression is rotated to without cut, crosses neutral silica gel post,
Obtain intermediate S4；Intermediate S3 is 1 with concentrated phosphoric acid mol ratio:3~6.
(5) under nitrogen protection, intermediate S4, raw material C, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine,
It is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows that no intermediate S4 is remained
Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, neutral silica gel post is crossed, in obtaining
Mesosome S5.In above-mentioned reaction, intermediate S4 is 1 with raw material C mol ratios:1~2；The mol ratio of intermediate S4 and sodium tert-butoxide is
1:1~3；Intermediate S4 and Pd2(dba)3Mol ratio be 1:0.01~0.05；Intermediate S4 and tri-butyl phosphine mol ratio
For 1:0.01~0.05；
(6) weigh intermediate S5 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 S5 acetic acid solution, 5h is stirred at room temperature, sample point plate, shows that no raw material S5 is remaining, 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, obtains intermediate S6；The mol ratio of the intermediate S5 and bromine is 1:1~1.5；
(7) under nitrogen protection, weigh intermediate S6 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, reacted
2h, reaction system is then risen to 0 DEG C, add 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, adds ether extraction, extraction
Liquid adds anhydrous magnesium sulfate and dried, and revolving, is recrystallized with alcohol solvent, obtains intermediate M2；The intermediate S6 and normal-butyl
The mol ratio of lithium is 1:1~1.5；The mol ratio of the intermediate S6 and triisopropyl borate ester are 1:1~1.5.
It is such by taking intermediate M2-3 synthesis as an example：
(1) in 250ml there-necked flask, 0.04mol raw material As, 100ml acetic acid is added, stirring and dissolving, then uses ice salt bath
It is cooled to 0 DEG C；By 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system,
After completion of dropwise addition, 20-25 DEG C of temperature control, stirring reaction 12 hours, sample point plate, show that no raw material I1-3 is remaining；After reaction terminates,
NaOH aqueous solution neutralization reaction liquid is added dropwise, adds dichloromethane extraction, layering, takes organic phase to filter, filtrate decompression is distilled to nothing
Cut, neutral silica gel post is crossed, obtains intermediate S1, HPLC purity 99.3%, yield 66.9%；
Elementary analysis structure (molecular formula C8H7BrO2)：Theoretical value C, 44.68；H,3.28；Br,37.16；Test value：C,
44.67；H,3.29；Br,37.16.ESI-MS(m/z)(M+)：Theoretical value 213.96, measured value 214.26.
(2) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.03mol intermediate S1,0.04mol raw materials
B-3,0.06mol sodium tert-butoxide, 0.0015mol Pd2(dba)3, 0.0015mol tri-butyl phosphines, 150ml toluene, mixing stirs
Mix, be heated to 115 DEG C, back flow reaction 24 hours, sample point plate, show that no raw material B-3 is remaining, reaction is complete；Naturally cool to
Room temperature, filtering, filtrate decompression rotate to without cut, cross neutral silica gel post, obtain intermediate S2-3, HPLC purity 99.3%, receive
Rate 60.9%；Elementary analysis structure (molecular formula C26H27NO2)：Theoretical value C, 81.01；H,7.06；N,3.63；Test value：C,
81.02；H,7.06；N,3.62.ESI-MS(m/z)(M+)：Theoretical value 385.20, measured value 385.80.
(3) in 250ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediate S2-3,100ml tetrahydrofurans
Stirring and dissolving, 0 DEG C is cooled to ice salt bath；The tetrahydrofuran solution (1.6M) of 63ml methyl-magnesium-bromides is slowly added dropwise, knot is added dropwise
Shu Hou, 20 DEG C of temperature control, stirring reaction 12 hours, sample point plate, show that no intermediate S2-3 is remaining, reaction is complete；By reaction solution
Filtering, filtrate decompression rotate to without cut, cross neutral silica gel post, obtain intermediate S3-3, HPLC purity 99.1%, yield
65.9%；Elementary analysis structure (molecular formula C27H31NO)：Theoretical value C, 84.11；H,8.10；N,3.63；Test value：C,
84.11；H,8.11；N,3.62.ESI-MS(m/z)(M+)：Theoretical value 385.24, measured value 386.01.
(4) in 500ml there-necked flask, lead under nitrogen protection, add the dense H of 0.04mol intermediates S3-3,200ml3PO4With
Water volume ratio is 1:3 mixed liquor, is stirred, 20 DEG C of temperature control, reacts 6 hours, sample point plate, shows that no intermediate S3-3 is remained
Remaining, reaction is complete；NaOH aqueous solution neutralization reaction liquid is added to pH=7, dichloromethane extraction is added, layering, takes organic phase mistake
Filter, filtrate decompression rotate to without cut, cross neutral silica gel post, obtain intermediate S4-3, HPLC purity 99.2%, yield
55.1%；Elementary analysis structure (molecular formula C27H29N)：Theoretical value C, 88.24；H,7.95；N,3.81；Test value：C,88.23；
H,7.95；N,3.82.ESI-MS(m/z)(M+)：Theoretical value 367.23, measured value 367.83.
(5) under nitrogen protection, intermediate S4-3, raw material C-1, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-tert
Phosphine, it is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows no intermediate
S4-3 is remaining, and reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam extremely without cut, crosses neutral silica gel post,
Obtain intermediate S5-3.In above-mentioned reaction, intermediate S4-3 is 1 with raw material C-1 mol ratios:1~2；Intermediate S4-3 and tertiary fourth
The mol ratio of sodium alkoxide is 1:1~3；Intermediate S4-3 and Pd2(dba)3Mol ratio be 1:0.01~0.05；Intermediate S4-3 with
The mol ratio of tri-butyl phosphine is 1:0.01~0.05；Elementary analysis structure (molecular formula C33H33N)：Theoretical value C, 89.34；H,
7.50；N,3.16；Test value：C,89.35；H,7.50；N,3.15.ESI-MS(m/z)(M+)：Theoretical value 443.26, actual measurement
It is worth for 443.66.
(6) 0.15mol intermediates S5-3,30ml 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, show that no intermediate S5-3 is remaining, reaction is complete；After reaction terminates, it is molten that sodium carbonate is added into reaction solution
Liquid neutralizes, and is extracted with dichloromethane, is layered, and takes organic phase, dry filter, and filtrate decompression rotates to without cut, crosses silicagel column, obtain
To intermediate S6-3, HPLC purity 98.6%, yield 61.3%.
Elementary analysis structure (molecular formula C33H32BrN)：Theoretical value C, 75.85；H,6.17；Br,15.29；N,2.68；Survey
Examination value：C,75.86；H,6.17；Br,15.29；N,2.67.ESI-MS(m/z)(M+)：Theoretical value 521.17, measured value are
522.17。
(7) 250ml there-necked flask, under the atmosphere for being passed through nitrogen, 0.08mol intermediates S6-3,40ml tetrahydrochysene furan is added
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, 0.096mol triisopropyl borate esters are added after 3h is reacted at -78 DEG C, 2h is reacted, reaction system is then risen to 0 DEG C, added
Entering 50mL 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, adds ether extraction, and extract adds anhydrous magnesium sulfate and dried,
Revolving, is recrystallized with alcohol solvent, obtains intermediate M2-3, purity 99.2%, yield 57.3%.
Elementary analysis structure (molecular formula C33H34BNO2)：Theoretical value C, 81.31；H,7.03；B,2.22；N,2.87；Test
Value：C,81.30；H,7.03；B,2.23；N,2.87.ESI-MS(m/z)(M+)：Theoretical value 487.27, measured value are
487.47。
When X is O atom：
(1) weigh raw material D 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 raw material D acetic acid solution, reaction is stirred at room temperature until reaction is complete；After reaction terminates, alkali is added into reaction solution
Liquid is neutralized, and is extracted with dichloromethane, is layered, takes organic phase to filter, and filtrate decompression is rotated to without cut, silicagel column is crossed, in obtaining
Mesosome S7；The raw material D and the molar ratio of bromine are 1:1~2；
(2) under nitrogen protection, weigh intermediate S7 and Cu powder to be added in ammoniacal liquor, be stirred, be then heated to 80
DEG C, react 2~6 hours, sample point plate, intermediate S7 is without residue for display；Naturally cool to room temperature, vacuum rotary steam, excessively neutral silicon
Glue post, obtain intermediate S8；In above-mentioned reaction, intermediate S7 and Cu mol ratio are 1:0.05~0.2, ammoniacal liquor is excessive, simultaneously
As reaction raw materials, acid binding agent and solvent；
(3) under nitrogen protection, intermediate S8, intermediate S9 (the same S8 of synthetic method), iodine, diethylene glycol (DEG) are sequentially added, is stirred
Mixing is mixed, is heated to 260~280 DEG C, is reacted 12~24 hours；Sample point plate, show that no intermediate S8 is remaining, reaction is complete；
After reaction terminates, room temperature is naturally cooled to, there is solid precipitation, filtered, filter cake is dried with vacuum drying chamber, then crosses neutral silica gel
Post, obtain intermediate S10；In above-mentioned reaction, intermediate S8 and intermediate S9 mol ratio is 1:1~2, intermediate S8 and iodine
Mol ratio is 1:0.05~0.1.
(4) under nitrogen protection, intermediate S10, raw material C, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine,
It is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows that no intermediate S10 is remained
Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, neutral silica gel post is crossed, in obtaining
Mesosome S11.In above-mentioned reaction, intermediate S10 is 1 with raw material C mol ratios:1~2；Intermediate S10 and sodium tert-butoxide mol ratio
For 1:1~3；Intermediate S10 and Pd2(dba)3Mol ratio be 1:0.01~0.05；Intermediate S10 and tri-butyl phosphine rub
You are than being 1:0.01~0.05；
(5) 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, shows that no raw material 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；
(6) 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, reaction system is then risen to 0 DEG C, add 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, adds ether extraction, extraction
Liquid adds anhydrous magnesium sulfate and dried, and revolving, is recrystallized with alcohol solvent, obtains intermediate M2；The intermediate S12 and normal-butyl
The mol ratio of lithium is 1:1~1.5；The mol ratio of the intermediate S12 and triisopropyl borate ester are 1:1~1.5.
It is such by taking intermediate M2-8 synthesis as an example：
(1) in 250ml there-necked flask, 0.04mol raw material D, 100ml acetic acid stirring and dissolvings is added, then use ice salt bath
It is cooled to 0 DEG C；By 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system,
After completion of dropwise addition, 20-25 DEG C of temperature control, stirring reaction 12 hours, sample point plate, show that no raw material D is remaining；After reaction terminates, drop
Add NaOH aqueous solution neutralization reaction liquid, add dichloromethane extraction, layering, take organic phase to filter, filtrate decompression is distilled to nothing and evaporated
Point, neutral silica gel post is crossed, obtains intermediate S7, HPLC purity 99.3%, yield 66.9%；
Elementary analysis structure (molecular formula C6H5BrO)：Theoretical value C, 41.65；H,2.91；Br,46.18；Test value：C,
41.64；H,2.91；Br,46.19.ESI-MS(m/z)(M+)：Theoretical value 171.95, measured value 173.05.
(2) in 250ml there-necked flask, lead under nitrogen protection, addition 0.04mol intermediate S7,0.004molCu powder,
100ml mass fractions are 30% ammoniacal liquor, are heated to 80 DEG C, insulation reaction 6 hours, sample point plate, show that no intermediate S7 is remained
Remaining, reaction is complete；Room temperature is naturally cooled to, then vacuum rotary steam crosses neutral silica gel post, obtains intermediate S8 extremely without cut,
HPLC purity 99.2%, yield 65.5%；
Elementary analysis structure (molecular formula C6H7NO)：Theoretical value C, 66.04；H,6.47；N,12.84；Test value：C,
66.03；H,6.47；N,12.85.ESI-MS(m/z)(M+)：Theoretical value 109.05, measured value 109.09.
(3) in 250ml there-necked flask, lead under nitrogen protection, add 0.05mol intermediates S8,0.06mol S9-2 (is closed
Into the same S8 of method), 0.005mol iodine, 80ml diethylene glycol (DEG) stirring and dissolvings, be heated to 270 DEG C, react 24 hours, sample point plate, show
Show that no intermediate S8 is remaining, reaction is complete；Room temperature is naturally cooled to, has solid precipitation after adding water, filters, takes filter cake to be done with vacuum
Dry case drying, then crosses neutral silica gel post, obtains intermediate S10-2, HPLC purity 99.1%, yield 58.5%；
Elementary analysis structure (molecular formula C24H23NO)：Theoretical value C, 84.42；H,6.79；N,4.10；Test value：C,
84.41；H,6.79；N,4.11.ESI-MS(m/z)(M+)：Theoretical value 341.18, measured value 341.68.
(4) under nitrogen protection, intermediate S10-2, raw material C-2, sodium tert-butoxide, Pd are weighed successively2(dba)3, three tertiary fourths
Base phosphine, is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown no intermediate
S10-2 is remaining, and reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam extremely without cut, crosses neutral silica gel post,
Obtain intermediate S11-2.In above-mentioned reaction, intermediate S10-2 is 1 with raw material C-2 mol ratios:1~2；Intermediate S10-2 and uncle
The mol ratio of sodium butoxide is 1:1~3；Intermediate S10-2 and Pd2(dba)3Mol ratio be 1:0.01~0.05；Intermediate S10-
2 with the mol ratio of tri-butyl phosphine be 1:0.01~0.05；
Elementary analysis structure (molecular formula C30H27NO)：Theoretical value C, 86.30；H,6.52；N,3.35；Test value：C,
86.31；H,6.52；N,3.34.ESI-MS(m/z)(M+)：Theoretical value 417.21, measured value 417.71.
(5) 0.15mol intermediates S11-2,30ml acetic acid is added in 100mL there-necked flask, is cooled with ice salt bath
To 0 DEG C；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,
Stir 5h；Sample point plate, show that no intermediate S11-2 is remaining, reaction is complete；After reaction terminates, carbonic acid is added into reaction solution
Sodium solution is neutralized, and is extracted with dichloromethane, is layered, and takes organic phase, dry filter, and filtrate decompression is rotated to without cut, crosses silica gel
Post, obtain intermediate S12-2, HPLC purity 98.6%, yield 61.3%.
Elementary analysis structure (molecular formula C30H26BrNO)：Theoretical value C, 72.58；H,5.28；Br,16.10；N,2.82；Survey
Examination value：C,72.57；H,5.28；Br,16.10；N,2.83.ESI-MS(m/z)(M+)：Theoretical value 495.12, measured value are
496.25。
(6) 250ml there-necked flask, under the atmosphere for being passed through nitrogen, 0.08mol intermediates S12-2,40ml tetrahydrochysene furan is added
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, 0.096mol triisopropyl borate esters are added after 3h is reacted at -78 DEG C, 2h is reacted, reaction system is then risen to 0 DEG C, added
Entering 50mL 2mol/L hydrochloric acid solutions, stir 3h, reaction is complete, adds ether extraction, and extract adds anhydrous magnesium sulfate and dried,
Revolving, is recrystallized with alcohol solvent, obtains intermediate M2-8, purity 99.2%, yield 57.3%.
Elementary analysis structure (molecular formula C30H28BNO3)：Theoretical value C, 78.10；H,6.12；B,2.34；N,3.04；Test
Value：C,78.10；H,6.12；B,2.33；N,3.05.ESI-MS(m/z)(M+)：Theoretical value 461.22, measured value are
461.42。
Concrete structure is as shown in table 1.
Table 1
Embodiment 2：The synthesis of compound 8
250mL there-necked flask, under the atmosphere for being passed through nitrogen, add 0.01mol intermediates M2-1,0.015mol raw material
M1-1, (90ml toluene, 45ml ethanol) is dissolved with mixed solvent, then add 0.03mol Na2CO3The aqueous solution (2M), lead to nitrogen
Stirring 1 hour, then add 0.0001mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is complete.Naturally it is cold
But, filter, filtrate revolving, cross silicagel column, obtain target product, purity 99.1%, yield 79.9%.Elementary analysis structure (point
Minor C52H38N2O)：Theoretical value C, 88.36；H,5.42；N,3.96；Test value：C,88.37；H,5.42；N,3.95.ESI-MS
(m/z)(M+)：Theoretical value 706.30, measured value 706.80.
Embodiment 3：The synthesis of compound 17：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-2 the preparation method of compound 17.
Elementary analysis structure (molecular formula C49H39NO)：Theoretical value C, 89.46；H,5.98；N,2.13；Test value：C,89.46；H,
5.98；N,2.14.ESI-MS(m/z)(M+)：Theoretical value 657.30, measured value 657.90.
Embodiment 4：The synthesis of compound 28：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-3 the preparation method of compound 28.
Purity 98.9%, yield 77.8%.Elementary analysis structure (molecular formula C52H45N)：Theoretical value C, 91.32；H,6.63；N,2.05；
Test value：C,91.32；H,6.64；N,2.04.ESI-MS(m/z)(M+)：Theoretical value 683.36, measured value 683.46.
Embodiment 5：The synthesis of compound 39：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-4 the preparation method of compound 39.
Purity 99.1%, yield 78.1%.Elementary analysis structure (molecular formula C55H44N2)：Theoretical value C, 90.13；H,6.05；N,3.82；
Test value：C,90.13；H,6.06；N,3.81.ESI-MS(m/z)(M+)：Theoretical value 732.35, measured value 732.95.
Embodiment 6：The synthesis of compound 50：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-5 the preparation method of compound 50.
Elementary analysis structure (molecular formula C52H38N2O)：Theoretical value C, 88.36；H,5.42；N,3.96；Test value：C,88.37；H,
5.42；N,3.95.ESI-MS(m/z)(M+)：Theoretical value 706.30, measured value 706.30.
Embodiment 7：The synthesis of compound 59：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-6 the preparation method of compound 59.
Elementary analysis structure (molecular formula C55H43NO)：Theoretical value C, 90.01；H,5.91；N,1.91；Test value：C,90.00；H,
5.91；N,1.92.ESI-MS(m/z)(M+)：Theoretical value 733.33, measured value 733.70.
Embodiment 8：The synthesis of compound 68：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-7 the preparation method of compound 68.
Elementary analysis structure (molecular formula C58H49N)：Theoretical value C, 91.66；H,6.50；N,1.84；Test value：C,91.67；H,6.50；
N,1.83。ESI-MS(m/z)(M+)：Theoretical value 759.39, measured value 759.56.
Embodiment 9：The synthesis of compound 80：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-8 the preparation method of compound 80.
Elementary analysis structure (molecular formula C55H43NO)：Theoretical value C, 90.01；H,5.91；N,1.91；Test value：C,90.00；H,
5.91；N,1.91.ESI-MS(m/z)(M+)：Theoretical value 733.33, measured value 733.93.
Embodiment 10：The synthesis of compound 90：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-9 the preparation method of compound 90.
Elementary analysis structure (molecular formula C55H43NO)：Theoretical value C, 90.01；H,5.91；N,1.91；Test value：C,90.01；H,
5.91；N,1.90.ESI-MS(m/z)(M+)：Theoretical value 733.33, measured value 733.83.
Embodiment 11：The synthesis of compound 99：
With embodiment 2, difference is to replace intermediate M2- using intermediate M2-10 the preparation method of compound 99
1.Elementary analysis structure (molecular formula C58H49N)：Theoretical value C, 91.66；H,6.50；N,1.84；Test value：C,91.65；H,
6.50；N,1.85.ESI-MS(m/z)(M+)：Theoretical value 759.39, measured value 759.99.
Embodiment 12：The synthesis of compound 111：
With embodiment 2, difference is to replace intermediate M2- using intermediate M2-11 the preparation method of compound 111
1.Elementary analysis structure (molecular formula C52H37NO2)：Theoretical value C, 88.23；H,5.27；N,1.98；Test value：C,88.22；H,
5.27；N,1.98.ESI-MS(m/z)(M+)：Theoretical value 707.28, measured value 707.58.
Embodiment 13：The synthesis of compound 124：
With embodiment 2, difference is to replace intermediate M2- using intermediate M2-12 the preparation method of compound 124
1.Elementary analysis structure (molecular formula C58H49N)：Theoretical value C, 91.66；H,6.50；N,1.84；Test value：C,91.65；H,
6.50；N,1.85.ESI-MS(m/z)(M+)：Theoretical value 759.39, measured value 759.41.
Embodiment 14：The synthesis of compound 131：
With embodiment 2, difference is to replace intermediate M2-1 using intermediate M2-3 the preparation method of compound 131
And intermediate M1-1 is replaced using intermediate M1-2.Elementary analysis structure (molecular formula C58H49N)：Theoretical value C, 91.66；H,
6.50；N,1.84；Test value：C,91.65；H,6.50；N,1.85.ESI-MS(m/z)(M+)：Theoretical value 759.39, actual measurement
It is worth for 760.41.
The organic compound of the present invention can be used as electronic blocking layer material in luminescent device, can also be used as luminous
Layer Subjective and Objective materials'use.The test of T1 energy level, hot property, HOMO energy levels is carried out to embodiment compound, as a result such as the institute of table 2
Show.
Table 2
| Compound | T1(ev) | Tg(℃) | Td(℃) | HOMO energy levels (ev) | Functional layer |
| Compound 28 | 2.77 | 143 | 413 | -5.84 | Luminescent layer |
| Compound 68 | 2.75 | 132 | 400 | -5.76 | Luminescent layer |
| Compound 99 | 2.75 | 137 | 408 | -5.78 | Luminescent layer |
| Compound 124 | 2.77 | 145 | 415 | -5.78 | Luminescent layer |
| Compound 131 | 2.75 | 139 | 407 | -5.83 | Luminescent layer |
| Compound 8 | 2.77 | 136 | 407 | -5.68 | Electronic barrier layer |
| Compound 17 | 2.77 | 144 | 416 | -5.69 | Electronic barrier layer |
| Compound 39 | 2.75 | 136 | 403 | -5.67 | Electronic barrier layer |
| Compound 50 | 2.75 | 143 | 413 | -5.68 | Electronic barrier layer |
| Compound 59 | 2.74 | 139 | 412 | -5.66 | Electronic barrier layer |
| Compound 80 | 2.76 | 132 | 400 | -5.66 | Electronic barrier layer |
| Compound 90 | 2.76 | 140 | 416 | -5.67 | Electronic barrier layer |
| Compound 111 | 2.76 | 137 | 408 | -5.68 | Electronic barrier layer |
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)
Measure, 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 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, organic compound of the present invention using fluorenes as core have higher triplet and higher heat endurance 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 1~13 and device comparative example 1
Application effect in part.Device embodiments 2~13 of the present invention, the device compared with device embodiments 1 of device comparative example 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 1~8 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 9~13 pairs of devices of example converts.The performance test results of each embodiment obtained device such as table 3
It is shown.
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 as hole injection layer 3；C) on hole injection layer 3, hole mobile material is deposited by vacuum evaporation mode
NPB, thickness 60nm, the layer are 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 8, thickness 20nm, the layer are electronic barrier layer 5；E) hair is deposited on electronic barrier layer 5
Photosphere 6, using CBP as material of main part, Ir (ppy)3As 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, thickness 40nm, this layer are deposited by vacuum evaporation mode
Organic material uses as hole barrier/electron transfer layer 7；G) on hole barrier/electron transfer layer 7, vacuum evaporation electricity
Sub- implanted layer LiF, thickness 1nm, the layer are electron injecting layer 8；H) on electron injecting layer 8, vacuum evaporation negative electrode Al
(100nm), the layer are negative electrode 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 17.Device embodiments 3：
The electronic blocking layer material of electroluminescent device is the compounds of this invention 39.Device embodiments 4：The electronics resistance of electroluminescent device
Barrier material is the compounds of this invention 50.Device embodiments 5：The electronic blocking layer material of electroluminescent device is chemical combination of the present invention
Thing 59.Device embodiments 6：The electronic blocking layer material of electroluminescent device is the compounds of this invention 80.Device embodiments 7：Electricity
The electronic blocking layer material of electroluminescence device is the compounds of this invention 90.Device embodiments 8：The electronic blocking of electroluminescent device
Layer material is the compounds of this invention 111.Device embodiments 9：The electronic blocking layer material of electroluminescent device is NPB, electroluminescent hair
The luminescent layer material of main part of optical device is changed into the compounds of this invention 68, and dopant material is Ir (ppy)3, Ir (ppy)3With compound 68
Mass ratio be 10:90.Device embodiments 10：The electronic blocking layer material of electroluminescent device is NPB, electroluminescent device
Luminescent layer material of main part is changed into the compounds of this invention 99, and dopant material is Ir (ppy)3, Ir (ppy)3With the mass ratio of compound 99
For 10:90.Device embodiments 11：The electronic blocking layer material of electroluminescent device is NPB, the luminescent layer master of electroluminescent device
Body material is changed into the compounds of this invention 124, and dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 124 is 10:
90.Device embodiments 12：The electronic blocking layer material of electroluminescent device is NPB, the luminous layer main body material of electroluminescent device
Material is changed into the compounds of this invention 28 and compound GHN, and dopant material is Ir (ppy)3, compound 28, GHN and Ir (ppy)3Three
Mass ratio is 60:30:10.Device embodiments 13：The electronic blocking layer material of electroluminescent device is NPB, electroluminescent cell
The luminescent layer material of main part of part is changed into the compounds of this invention 131 and compound GHN, and dopant material is Ir (ppy)3, compound
131st, GHN and Ir (ppy)3Three's mass ratio is 60:30:10.Device comparative example 1：The electronic barrier layer of electroluminescent device
Material is NPB, and the luminescent layer material of main part of electroluminescent device is known compound CBP, and dopant material is Ir (ppy)3, Ir
(ppy)3Mass ratio with CBP is 10:90.After the making of above-mentioned electroluminescent device, the current efficiency of measurement device and life-span,
It the results are shown in Table shown in 3.
Table 3
| Numbering | Current efficiency (cd/A) | Color | LT95 life-spans (Hr)@5000nits |
| Device embodiments 1 | 42.1 | Green glow | 37.5 |
| Device embodiments 2 | 40.1 | Green glow | 39.9 |
| Device embodiments 3 | 41.5 | Green glow | 43.7 |
| Device embodiments 4 | 44.2 | Green glow | 41.9 |
| Device embodiments 5 | 41.3 | Green glow | 39.8 |
| Device embodiments 6 | 43.5 | Green glow | 39.7 |
| Device embodiments 7 | 39.6 | Green glow | 37.5 |
| Device embodiments 8 | 41.9 | Green glow | 35.4 |
| Device embodiments 9 | 48.9 | Green glow | 38.2 |
| Device embodiments 10 | 48.2 | Green glow | 40.5 |
| Device embodiments 11 | 49.1 | Green glow | 42.9 |
| Device embodiments 12 | 58.9 | Green glow | 62.8 |
| Device embodiments 13 | 59.6 | Green glow | 67.8 |
| Device comparative example 1 | 28 | Green glow | 10.5 |
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 3
Make, and compared with device comparative example 1, either efficiency or life-span obtain larger change than known OLED material, 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
1~13 and device comparative example 1 carry out high temperature driven life tests at 85 DEG C, acquired results are as shown in table 4.
Table 4
It was found from the data of table 4, device embodiments 1~13 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, OLED provided by the invention has the driving life-span well.
In order to compare the different components situation that efficiency decays at higher current densities, efficiency attenuation coefficient is definedCarry out table
Show；
It represents that driving current is 100mA/cm2When device maximal efficiency μ100With the maximal efficiency μ of devicemaxDifference with
Ratio between maximal efficiency,Value is bigger, illustrates that the efficiency roll-off of device is more serious, conversely, explanation device is in high current density
The problem of drop that quickly declines down, is under control.
The organic compound of the present invention uses in luminescent device, can be used as electronic blocking layer material, can also conduct
Luminescent layer material of main part uses.Line efficiency attenuation coefficient is entered respectively to device embodiments 1~13 and device comparative example 1Measure,
Testing result is as shown in table 5.
Table 5
It was found from the data of table 5, compared with device comparative example 1, OLED provided by the invention is at higher current densities
With shallower efficiency roll-off trend, good prospect is provided for industrialization.
Work limitation rate is also more stable at low temperature for OLED prepared by further material of the present invention, and device is real
Apply example 3,9,13 and device comparative example 1 and carry out efficiency test in -10~80 DEG C of sections, acquired results are as shown in table 6 and Fig. 2.
Table 6
It was found from table 6 and Fig. 2 data, device embodiments 3,9,13 are material of the present invention and the device of known materials collocation
Structure, compared with device comparative example 1, not only Efficiency at Low Temperature is high, and in temperature elevation process, efficiency steadily raises.
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., it should be included in the scope of the protection.
Claims (9)
1. a kind of fluorenes class organic compound, it is characterised in that shown in the structure of the organic compound such as formula (1)：
In formula (1), Ar1It is expressed as substituted or unsubstituted C6-60Aryl, do not take containing one or more heteroatomic substitutions or
5~60 unit's heteroaryls in generation；The hetero atom is nitrogen, oxygen or sulphur；
Ar2It is expressed as singly-bound, substituted or unsubstituted C6-60Arlydene, contain one or more heteroatomic substitutions or unsubstituted
5~60 yuan of heteroarylidenes；The hetero atom is nitrogen, oxygen or sulphur；
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 the imido grpup of alkyl, alkyl-substituted imido grpup or aryl substitution；
Ar3It is expressed as substituted or unsubstituted C6-60Aryl, contain one or more heteroatomic substituted or unsubstituted 5-60 members
Heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；
In formula (2), R1It is expressed as structure shown in formula (3)；
In formula (3), X1、X2The alkylene for being expressed as oxygen atom, sulphur atom, C1-10 straight or branched alkyls and substituting independently
One kind in base, the alkylidene of aryl substitution, alkyl-substituted imido grpup or the imido grpup of aryl substitution；Formula (3) passes through CL1-
CL2Key, CL2-CL3Key or CL3-CL4Key and formula (2) connection.
2. fluorenes class organic compound according to claim 1, it is characterised in that Ar2Be expressed as phenylene, sub- dibiphenylyl,
Sub- terphenyl, naphthylene, anthrylene, phenanthrylene, sub- pyrenyl, furylidene, sub- thienyl, sub- pyridine radicals, sub- pyrimidine radicals, Asia
One kind in pyridazinyl, sub- pyrazinyl or sub- triazine radical, Ar2It is also shown as singly-bound；Ar1And Ar3Independently be expressed as benzene
Base, dibiphenylyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, thienyl, pyridine radicals, pyrimidine radicals, pyridazinyl,
One kind in pyrazinyl or triazine radical.
3. fluorenes class organic compound according to claim 1, it is characterised in that the formula (2) is expressed as：
Any one.
4. fluorenes class organic compound according to claim 1, it is characterised in that the concrete structure formula of the organic compound
For：
In any one.
5. the preparation method of the fluorenes class organic compound described in a kind of any one of Claims 1 to 4, it is characterised in that prepared
The reaction equation occurred in journey is：
Specifically preparation method is：Intermediate M1 and intermediate M2 are weighed, is 1.5~3 with volume ratio:1 toluene ethanol mixing is molten
Agent is dissolved；Add Na2CO3The aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction
Reacted 10~24 hours at 90~110 DEG C of temperature, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target production
Thing；
The intermediate M1 and intermediate M2 mol ratio is 1:1.0~1.5；Pd(PPh3)4Mol ratio with intermediate M1 is
0.006~0.02:1, Na2CO3Mol ratio with intermediate M1 is 2.0~3.0:1.
6. a kind of fluorenes class organic compound as described in any one of Claims 1 to 4 is used to prepare organic electroluminescence device.
7. 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 fluorenes class organic compound described in any one of Claims 1 to 4.
8. 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 fluorenes class organic compound described in 1~4 any one.
9. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that the luminescent layer, which contains Claims 1 to 4, appoints
Fluorenes class organic compound described in one.
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| CN114315742A (en) * | 2021-12-21 | 2022-04-12 | 湖北尚赛光电材料有限公司 | Fluorene-containing compound and application thereof |
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| CN107057681A (en) * | 2016-04-25 | 2017-08-18 | 中节能万润股份有限公司 | A kind of photoelectric material containing xanthene structure and its application in OLED fields |
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| KR20140130297A (en) * | 2013-04-30 | 2014-11-10 | (주)피엔에이치테크 | Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same |
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