CN110272380A - It is a kind of using spiro fluorene as the compound of core, preparation method and its application in organic electroluminescence device - Google Patents

It is a kind of using spiro fluorene as the compound of core, preparation method and its application in organic electroluminescence device Download PDF

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CN110272380A
CN110272380A CN201810210418.3A CN201810210418A CN110272380A CN 110272380 A CN110272380 A CN 110272380A CN 201810210418 A CN201810210418 A CN 201810210418A CN 110272380 A CN110272380 A CN 110272380A
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layer
expressed
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unsubstituted
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庞羽佳
李崇
张兆超
张小庆
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Jiangsu Sunera Technology Co Ltd
Jiangsu Sanyue Optoelectronic 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 spiro fluorene as the compound of core, preparation method and its application in organic electroluminescence device, the compound is using spiro fluorene as core, connect electron-donating group and electron-withdrawing group, it is easy to accomplish electronic blocking, to be easier to obtain the high efficiency of device.The compound of the present invention glass transition temperature with higher and molecule thermal stability, suitable HOMO and lumo energy, are optimized by device architecture, can effectively promote the photoelectric properties of OLED device and the service life of OLED device.

Description

It is a kind of to be sent out using spiro fluorene as the compound of core, preparation method and its in organic electroluminescence Application in optical device
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of using spiro fluorene as the compound of core, its preparation side Method and its application in organic electroluminescence device.
Background technique
Organic electroluminescent (Organic Light Emission Diodes, OLED) 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.
Structure of the OLED luminescent device like sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various different function materials are overlapped mutually depending on the application collectively constitutes OLED luminescent device together. As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer functional material Positive and negative charge in film layer, 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 of OLED device, use The performances such as service life also need further to be promoted.
Proposing high performance research for OLED luminescent device includes: the driving voltage for reducing device, improves shining for device Efficiency improves the service life etc. of device.In order to realize OLED device performance continuous promotion, not only need from OLED device The innovation of structure and manufacture craft is constantly studied and is innovated with greater need for oled light sulfate ferroelectric functional material, formulates out higher performance OLED functional material.
Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two major classes, i.e. charge injection transmission from purposes Material and luminescent material further can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material Luminescent material, can also be divided into main body luminescent material and dopant material by material, hole injection transmission material and hole barrier materials.
In order to make high performance OLED luminescent device, it is desirable that various organic functional materials have good photoelectric characteristic, 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 requires material to have 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, electronics biography A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is infused including at least hole Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form with rich and more The characteristics of sample.In addition, used photoelectric functional material has stronger for the collocation of the OLED device of different structure Selectivity, performance of the identical material in different structure device, it is also possible to 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, OLED functional material with high performance or combination of materials, is just able to achieve device High efficiency, the overall characteristic of long-life and low-voltage.With regard to current OLED show and the actual demand of Lighting Industry for, at present The development of OLED material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as material enterprise development higher performance Organic functional material is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides one kind using spiro fluorene as core compound, its preparation Method and its application in organic electroluminescence device.The compound of the present invention contains spiro fluorene structure, glass with higher Change temperature and molecule thermal stability, suitable lumo energy, can be used as electronic blocking layer material applied to Organic Light Emitting Diode On, there are good photoelectric properties, can satisfy OLED device enterprise, especially OLED display panel and OLED Illumination Enterprise Demand.
Technical scheme is as follows:
One aspect of the present invention provides a kind of using spiro fluorene as the compound of core, the structure of the compound such as general formula (1) institute Show:
Wherein, R1For electron-withdrawing group, be expressed as pyridyl group, quinolyl, isoquinolyl, phenanthroline base, benzimidazolyl, One of benzoxazolyl, pyrido indyl, quinoxalinyl, triazine radical, alternatively, one or more H in above-mentioned group Atom can be by D, F, C1-10Linear or branched alkyl group, C6-20Aryl, C5-20Heteroaryl replaces；
R2For electron-donating group, it is expressed as structure shown in general formula (2), general formula (3) or general formula (4):
Wherein, Ar1It is expressed as singly-bound, substituted or unsubstituted C6-30Arlydene contains one or more heteroatomic substitutions Or unsubstituted 5~30 yuan of heteroarylidenes；The hetero atom is N, O or S；
R3、R4Separately it is expressed as substituted or unsubstituted C6-60Aryl, substituted or unsubstituted 5-60 member heteroaryl Base；The hetero atom is N, O or S；
R5、R6Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 member heteroaryl Base；The hetero atom is N, O or S；R5、R6With substituent group or simultaneously loop type is connected with phenyl ring；
X is expressed as singly-bound, O, S or ethenylidene；
X1 is expressed as the imido grpup that the methylene that O, S, Se, alkyl-substituted methylene, aryl replace or aryl replace.
Further, R1It is expressed as any one of structural formula:
Further, R2It is expressed as any one of structural formula:
Further, the concrete structure formula of the general formula (1) is following any:
Another aspect of the present invention provides one kind as described above using spiro fluorene as the preparation method of the compound of core, including Following steps:
Step 1: synthetic intermediate II
By raw material I and boronic acid compounds R1-B(OH)2It is dissolved with toluene, Pd (PPh is added3)4And sodium carbonate, in indifferent gas Under atmosphere, by above-mentioned mixed solution in 95~110 DEG C, react 10~24 hours, cooled to room temperature, and filtering reacting solution, Filtrate carries out vacuum rotary steam, crosses neutral silica gel column, obtains intermediate II；
The reaction equation occurred in step 1 is as follows:
Step 2: synthesising target compound
By intermediate II and R2- H is dissolved with toluene；Add Pd2(dba)3, tri-tert-butylphosphine, sodium tert-butoxide；In inertia Under atmosphere, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 95-110 DEG C, cooling and filtering reacting solution, filter Liquid revolving, crosses silicagel column, obtains target compound；
The reaction equation occurred in step 2 is as follows:
Further, in step 1, the toluene dosage is that every 1g raw material I 30-50mL toluene dissolves；The raw material I with The molar ratio of boronic acid compounds is 1:(1.0~1.5)；Pd (the PPh3)4Molar ratio with raw material I is (0.005~0.01): 1, the molar ratio of the sodium carbonate and raw material I is (1.5~3.0): 1；In step 2, the intermediate II and R2The molar ratio of-H For 1:(1.0~1.5), Pd2(dba)3It is (0.006~0.02) with the molar ratio of intermediate II: 1, tri-tert-butylphosphine and intermediate II molar ratio is (0.006~0.02): 1, the molar ratio of sodium tert-butoxide and intermediate II is (2.0~3.0): 1.
It is as described above the compound of core in organic electroluminescence device using spiro fluorene the present invention also provides one kind Application.
The present invention also provides a kind of organic electroluminescence devices, comprising: first electrode, second electrode and is set to institute At least one layer of organic film between first electrode and second electrode is stated, the organic film material therefor contains as described above Using spiro fluorene as the compound of core；The first electrode and second electrode are respectively anode and cathode.
Further, the organic film includes hole transmission layer, luminescent layer and is set to hole transmission layer and shines Electronic barrier layer between layer, the electronic barrier layer material therefor contain as described above using spiro fluorene as the compound of core.
Further, the luminescent layer is made of material of main part and dopant material, the material of main part of the luminescent layer, described Meet following relationship between the dopant material of luminescent layer and the electronic barrier layer material therefor:
A) Shu HOMOElectronic barrier layer-HOMOLuminescent layer material of main partShu≤0.4eV；
B) Shu LUMOElectronic barrier layer-LUMOLuminescent layer material of main partShu >=0.2eV；
C) Shu LUMOElectronic barrier layer-LUMOLuminescent layer dopant materialShu >=0.2eV；
d)T1 electronic barrier layer≥2.6eV。
Further, shown in the structural formula such as general formula (5) of the hole transmission layer material therefor:
Wherein, D1、D2、D3Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3-50 Circle heterocyclic ring aryl；The preferred structure formula of the general formula (5) is as follows:
Further, the organic film further includes electron transfer layer and hole injection layer, the hole transmission layer, electronics Barrier layer and luminescent layer are set in turn between electron transfer layer and hole injection layer, and sequence is as follows: hole injection layer, hole pass Defeated layer, electronic barrier layer, luminescent layer, electron transfer layer, the structural formula of the electron transfer layer material therefor are general formula (6)- Any one of (10):
Wherein, E1-E10Separately it is expressed as C1-30Alkyl, the C of linear or branched alkyl group substitution1-30Linear chain or branched chain Alkyl-substituted alkoxy, substituted or unsubstituted C6-40Aryl, substituted or unsubstituted 3-30 circle heterocyclic ring aryl, alternatively, E1- E10Separately it is expressed as H and E1-E10It is not simultaneously H；
The preferred structure formula of the general formula (6) are as follows:
General formula (7) the preferred structure formula are as follows:
General formula (8) the preferred structure formula are as follows:
General formula (9) the preferred structure formula are as follows:
General formula (10) the preferred structure formula are as follows:
Further, the structural formula of the hole injection layer material therefor is any in general formula (11), (12) or (13) Kind:
Wherein, F1-F3Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3-30 member Heteroaryl；
G1-G6Separately it is expressed as itrile group, halogen atom, amide groups, alkoxy, ester group, nitro, C1-30Straight chain or branch Carbon atom, the substituted or unsubstituted C of alkyl group substitution6-30Aryl, 3-30 circle heterocyclic ring aryl, alternatively, G1-G6Separately It is expressed as H and is not simultaneously H；
The preferred structure formula of general formula (11) are as follows:
General formula (12) the preferred structure formula are as follows:
General formula (13) the preferred structure formula are as follows:
Further, the material of main part of the luminescent layer is the compound containing anthryl, structural formula such as general formula (14) institute Show:
Wherein, B1-B8Separately it is expressed as H, C1-30Alkyl, the C of linear or branched alkyl group substitution1-30Straight chain or branch Alkoxy, the substituted or unsubstituted C of alkyl group substitution6-30Aryl, substituted or unsubstituted 3-30 circle heterocyclic ring aryl；B9、B10 Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3-30 unit's heteroaryl；The general formula (14) preferred structure formula is listed below:
Further, shown in the structural formula of the dopant material of the luminescent layer such as general formula (15):
Wherein, any one of M Pt, Ir, Os or Cu；X2、X3、X4、X5Separately it is expressed as in O, C or N It is a kind of；A5、A6Separately it is expressed as aryl；A7For organic ligand；n1=0,1,2 or 3；n2=1,2 or 3；General formula (15) Preferred structure formula can be listed below:
Further, the organic film further includes electron injecting layer, and the electron injecting layer material is lithium, lithium salts or caesium One of salt；The lithium salts is one of 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or Lithium Azide；The cesium salt is One of cesium fluoride, cesium carbonate or cesium azide.
The present invention also provides a kind of display original sets, contain organic electroluminescence device as described above.
The present invention is beneficial to be had the technical effect that
1, the compound of the present invention connects electron-donating group and electron-withdrawing group using spiro fluorene as core, has three high lines State energy level (T1), the electronic barrier layer materials'use as OLED luminescent device can effectively stop the exciton energy of luminescent layer to transmit Into hole transmission layer, combined efficiency of the exciton in luminescent layer is improved, capacity usage ratio is improved, imitated to improve device and shine Rate.
2, the compound of the present invention makes electrons and holes in luminescent layer as the electronic barrier layer of OLED luminescent device Distribution more balances, and under appropriate HOMO energy level, improves hole injection and transmission performance；Under suitable lumo energy, Play the role of electronic blocking again, promotes combined efficiency of the exciton in luminescent layer；Exciton utilization rate and height can be effectively improved Fluorescent radiation efficiency reduces the efficiency roll-off under high current density, reduces device voltage, improves current efficiency and the longevity of device Life；To be easier to obtain the high efficiency of device.
3, the present invention using spiro fluorene as the compound of core as OLED luminescent device electronic blocking layer material when, device Current efficiency, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.Into One step, on OLED device layer structure matching, after introducing hole and electron injecting layer, makes transparent anode, metallic cathode and have Machine material interface is more stable, hole, electron injection effect promoting；Hole transmission layer again can lamination be two or more layers, it is adjacent The hole transmission layer for connecing hole injection layer side plays the role of hole transport and reduces exciton transfer barrier；Electron transfer layer is again Can lamination be two or more layers, the electron transfer layer of adjacent luminescent layer side can be named as hole blocking layer (HBL) again, provide Hole barrier effect promotes exciton combined efficiency in luminescent layer, and the electron transfer layer of adjacent electron injecting layer side then plays Electron-transport and the effect for reducing exciton transfer barrier.It should be mentioned, however, that each of these layers are not necessarily present.
4, used in OLED device it is of the invention using spiro fluorene as the compound of core after, the driving voltage of device reduces, Current efficiency, power efficiency, external quantum efficiency are further enhanced, and it is obvious that device lifetime promotes effect.Illustrate of the invention Compound has good application effect in OLED luminescent device, has good industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the invention for being applied to OLED device using spiro fluorene as the compound of core；
Fig. 2 is the current efficiency variation with temperature curve of the OLED device of the compound of the present invention preparation；
Description of symbols: 1-transparent substrate layer；2-ito anode layers；3-hole injection layers；4-hole transmission layers； 5-electronic barrier layers；6-luminescent layers；7-electron transfer layers；8-electron injecting layers；9-cathode reflection electrode layers.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below with reference to embodiment, illustrated embodiment is served only for explaining this hair It is bright, it is not intended to limit the scope of the present invention.
In following embodiments, comparative example, reagent, material and the instrument used such as not special explanation, It is commercially available for conventional reagent, conventional material and conventional instrument, involved in reagent can also be by being conventionally synthesized Method synthesis obtains.
The present invention is described using spiro fluorene as the preparating example of the compound of core below by embodiment 1, and there is same general formula Compound be distinguish with Arabic numerals, such as raw material A 1, raw material A 2, raw material B1, raw material B2, intermediate C1, intermediate C2 etc..
Embodiment 1 is using spiro fluorene as the preparation of the compound of core
The preparation of embodiment 1-1 compound 3
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol raw material A 1,0.015mol raw material B1 is added, with mixed Bonding solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C1, HPLC purity 94.1%, yield 76.6%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C1,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains target production Object, HPLC purity 92.3%, yield 65.9%.
Elemental analysis structure (molecular formula C52H34N4): theoretical value C, 87.37；H,4.79；N,7.84；Test value: C, 87.38；H,4.78；N,7.84.HRMS (EI): theoretical value 700.26, measured value 700.46.HRMS (EI): theoretical value is 714.28 measured value 714.17.
The preparation of embodiment 1-2 compound 5
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol raw material A 2,0.015mol raw material B1 is added, with mixed Bonding solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C2, HPLC purity 95.4%, yield 73.0%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C2,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150ml toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains target production Object, HPLC purity 97.4%, yield 76.5%.
Elemental analysis structure (molecular formula C52H34N4): theoretical value C, 87.37；H,4.79；N,7.84；Test value: C, 87.36；H,4.79；N,7.85.HRMS (EI): theoretical value 700.26, measured value 700.46.HRMS (EI): theoretical value is 714.28 measured value 714.25.
The preparation of embodiment 1-3 compound 10
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol raw material A 3,0.015mol raw material B1 is added, with mixed Bonding solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C3, HPLC purity 93.5%, yield 76.3%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C3,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains target production Object, HPLC purity 92.7%, yield 69.6%.
Elemental analysis structure (molecular formula C52H34N4): theoretical value C, 87.37；H,4.79；N,7.84；Test value: C, 87.38；H,4.78；N,7.84.HRMS (EI): theoretical value 700.26, measured value 700.29.
The preparation of embodiment 1-4 compound 23
Step 1: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol raw material A 4,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains intermediate C4, HPLC purity 92.5%, yield 76.1%；
Step 2: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol intermediate C4,0.015mol raw material B3 is added, uses Mixed solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 95.7%, yield 72.1%.
Elemental analysis structure (molecular formula C48H32N2): theoretical value C, 90.54；H,5.07；N,4.40；Test value: C, 90.53；H,5.08；N,4.40.HRMS (EI): theoretical value 636.26, measured value 636.31.
The preparation of embodiment 1-5 compound 31
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol raw material A 3,0.015mol raw material B4 is added, with mixed Bonding solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C5, HPLC purity 91.8%, yield 72.4%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C5,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains target production Object, HPLC purity 96.8%, yield 75.9%.
Elemental analysis structure (molecular formula C56H37N3): theoretical value C, 89.45；H,4.96；N,5.59；Test value: C, 89.46；H,4.95；N,5.59.HRMS (EI): theoretical value 751.30, measured value 751.36.
The preparation of embodiment 1-6 compound 33
Step 1: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol raw material A 5,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains intermediate C6, HPLC purity 93.4%, yield 77.1%.
Step 2: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol intermediate C6,0.015mol raw material B5 is added, uses Mixed solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 90.8%, yield 76.8%.
Elemental analysis structure (molecular formula C56H37N3): theoretical value C, 89.45；H,4.96；N,5.59；Test value: C, 89.46；H,4.95；N,5.59.HRMS (EI): theoretical value 751.30, measured value 751.21.
The preparation of embodiment 1-7 compound 36
Step 1: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol raw material A 4,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150ml toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains intermediate C7, HPLC purity 92.8%, yield 74.6%；
Step 2: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol intermediate C7,0.015mol raw material B6 is added, uses Mixed solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 93.7%, yield 69.2%.
Elemental analysis structure (molecular formula C56H37N3): theoretical value C, 89.45；H,4.96；N,5.59；Test value: C, 89.46；H,4.96；N,5.58.HRMS (EI): theoretical value 751.30, measured value 751.36.
The preparation of embodiment 1-8 compound 41
Step 1: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol raw material A 6,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains intermediate C8, HPLC purity 92.6%, yield 68.5%；
Step 2: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol intermediate C8,0.015mol raw material B7 is added, uses Mixed solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, fully reacting.Natural cooling, filtering, Filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 96.8%, yield 74.8%.
Elemental analysis structure (molecular formula C56H37N3): theoretical value C, 89.45；H,4.96；N,5.59；Test value: C, 89.44；H,4.97；N,5.59.HRMS (EI): theoretical value 751.30, measured value 751.42.
The preparation of embodiment 1-9 compound 50
Step 1: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol raw material A 6,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains intermediate C9, HPLC purity 94.9%, yield 79.5%；
Step 2: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol intermediate C9,0.015mol raw material B8 is added, uses Mixed solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 93.4%, yield 77.8%.
Elemental analysis structure (molecular formula C56H37N3): theoretical value C, 89.45；H,4.96；N,5.59；Test value: C, 89.45；H,4.95；N,5.60.HRMS (EI): theoretical value 751.30, measured value 751.38.
The preparation of embodiment 1-10 compound 73
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol raw material A 6,0.015mol raw material B9 is added, with mixed Bonding solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C10, HPLC purity 93.8%, yield 71.1%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C10,0.015mol raw material B10, (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, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 91.3%, yield 76.7%.
Elemental analysis structure (molecular formula C55H37N): theoretical value C, 92.79；H,5.24；N,1.97；Test value: C, 92.78；H,5.25；N,1.97.HRMS (EI): theoretical value 711.29, measured value 711.26.
The preparation of embodiment 1-11 compound 82
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.01mol raw material A 6 is added, 0.015mol raw material B11, uses Mixed solvent dissolves (90mL toluene, 45mL ethyl alcohol), and 0.03mol Na is then added2CO3It is small to lead to nitrogen gas stirring 1 for aqueous solution (2M) When, 0.0001mol Pd (PPh is then added3)4, it is heated to reflux 15 hours, samples contact plate, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C11, HPLC purity 92.5%, yield 74.5%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C11,0.015mol raw material B12, (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, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 92.6%, yield 78.2%.
Elemental analysis structure (molecular formula C70H47N3): theoretical value C, 90.39；H,5.09；N,4.52；Test value: C, 90.38；H,5.10；N,4.52.HRMS (EI): theoretical value 929.38, measured value 929.22.
The preparation of embodiment 1-12 compound 113
Step 1: being passed through nitrogen in the there-necked flask of 250mL, 0.02mol raw material B13,40mL tetrahydrofuran is added and has dissolved Entirely, -78 DEG C are cooled to, the tetrahydrofuran solution of the 1.6mol/L n-BuLi of 15mL is then added into reaction system, -78 0.024mol triisopropyl borate ester is added after reacting 3h at DEG C, reacts 2h, reaction system is then risen to 0 DEG C, is added 50mL's 2mol/L hydrochloric acid solution stirs 3h, and ether extraction is added in fully reacting, and extract liquor is added anhydrous magnesium sulfate drying, rotates, uses Alcohol solvent recrystallization, obtains intermediate C8, HPLC purity 93.8%, yield 71.6%；
Step 2: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol raw material A 1,0.015mol intermediate C12, (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, natural cooling after fully reacting, mistake Filter, filtrate revolving, crosses silicagel column, obtains intermediate C13, HPLC purity 94.9%, yield 75.6%；
Step 3: be passed through nitrogen in the there-necked flask of 250mL, be added 0.01mol intermediate C13,0.015mol raw material B2, 0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene are heated to 95 DEG C, Back flow reaction 24 hours, contact plate is sampled, natural cooling after fully reacting filters, and filtrate revolving crosses silicagel column, obtains target production Object, HPLC purity 97.9%, yield 68.9%.
Elemental analysis structure (molecular formula C54H35N3): theoretical value C, 89.35；H,4.86；N,5.79；Test value: C, 89.36；H,4.856；N,5.79.HRMS (EI): theoretical value 725.28, measured value 725.31.
This organic compound uses in luminescent device, has high Tg (glass transition temperature) and singlet energy level (S1), suitable HOMO, lumo energy can be used as the use of luminescent layer material of main part.To the compounds of this invention and current material point Not carry out hot property, singlet energy level, triplet and HOMO energy level test, the results are shown in Table 1.
Table 1
Compound T1(ev) Lumo energy (ev) HOMO energy level (eV)
Compound 2 2.75 2.33 5.75
Compound 5 2.72 2.30 5.69
Compound 10 2.76 2.31 5.73
Compound 23 2.74 2.29 5.77
Compound 31 2.77 2.27 5.76
Compound 33 2.70 2.33 5.71
Compound 36 2.67 2.35 5.77
Compound 41 2.72 2.29 5.70
Compound 50 2.74 2.34 5.76
Compound 73 2.71 2.31 5.78
Compound 82 2.68 2.30 5.75
Compound 113 2.78 2.27 5.74
GH1 2.79 3.0 5.9
GH2 2.86 2.58 6.01
GH3 2.67 2.73 6.02
GD1 - 3.07 5.43
EB1 2.67 2.36 5.66
Note: triplet T1It is to be tested by the F4600 Fluorescence Spectrometer of Hitachi, the test condition of material is 2*10-5's Toluene solution；Highest occupied molecular orbital HOMO energy level is tested by ionizing energy test macro (IPS3), is tested as big compression ring Border.Lumo energy is the energy of UV absorption initial position and the difference of HOMO energy level.
By upper table data it is found that comparing emitting layer material, HOMO energy level difference≤0.4ev, lumo energy difference >=0.2ev, and And there is high triplet, it can effectively stop electronics and energy loss.Therefore, organic material of the present invention is as electronic blocking Layer material is applied to OLED device, can effectively improve the luminous efficiency and service life of device.
By the following examples 2 the present invention will be described in detail synthesis be the compound of core in OLED device using spiro fluorene Application effect.In each embodiment and comparative example that embodiment 2 is included, the manufacture craft of device is identical, and uses The film thickness of identical baseplate material and electrode material, electrode material is also consistent, except that device stack structure, collocation Material and thicknesses of layers are different.Device stack structure is as shown in table 2, and the structural formula of critical materials used is as shown in table 3, respectively The performance test results of device are shown in Table 4.
The preparation of 2 OLED device of embodiment
The preparation of embodiment 2-1 device 1
As shown in Figure 1, a kind of electroluminescent device, preparation step include:
A) the ito anode layer 2 on transparent substrate layer 1 is cleaned, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively Minute, then handled 2 minutes in plasma cleaner；
B) on ito anode layer 2, HI1, evaporation thickness 10nm are deposited by vacuum evaporation mode, which is hole note Enter layer 3；
C) on hole injection layer 3, HT1, evaporation thickness 70nm are deposited by vacuum evaporation mode, which is hole biography Defeated layer 4；
D) on hole transmission layer 4, the compound 2 of preparation of the embodiment of the present invention, vapor deposition are deposited by vacuum evaporation mode With a thickness of 10nm, which is electronic barrier layer 5；
E) luminescent layer 6 is deposited on electronic barrier layer 5, uses compound GH1 as material of main part, GD1 is as doping The mass ratio of material, GD1 and GH1 are 10:90, evaporation thickness 30nm；
F) on luminescent layer 6, ET2 and EI1 are deposited by vacuum evaporation mode, the mass ratio of ET2 and EI1 are 1:1, are steamed With a thickness of 35nm, which is electron transfer layer 7 for plating；
G) on electron transfer layer 7, vacuum evaporation LiF, evaporation thickness 1nm, the layer are electron injecting layer 8；
H) on electron injecting layer 8, vacuum evaporation cathode Al is as cathode reflection electrode layer 10, evaporation thickness 100nm obtains device 1.
Table 2
Table 3
After the production for completing electroluminescent device according to above-mentioned steps, measurement device is in 10mA/cm2Electricity under current density Efficiency and service life are flowed, the result is shown in shown in table 4.
Table 4
Note: life-span test system is owner of the present invention and the OLED device life test that Shanghai University is studied jointly Instrument.
In order to compare different components at higher current densities efficiency decay the case where, define efficiency attenuation coefficient φ carry out table Show, it indicates that driving current is 100mA/cm2When device maximal efficiency μ100With the maximal efficiency μ of devicemDifference and maximum imitate Rate μ100Between ratio, φ value is bigger, illustrates that the efficiency roll-off of device is more serious, conversely, illustrating device at higher current densities The problem of dropping of quickly declining is under control.The present invention determines the efficiency attenuation coefficient φ of device 1-12 and device comparative example 1, knot Fruit is as shown in table 5:
Table 5
From the point of view of 5 data of table, compared by the efficiency attenuation coefficient of embodiment and comparative example it will be seen that using this The organic luminescent device of the compound preparation of invention has lesser efficiency attenuation coefficient, illustrates using the compound of the present invention system Standby organic electroluminescence device can be effectively reduced efficiency roll-off.
Work limitation rate is also more stable at low temperature for the OLED device of material preparation of the present invention, by device 1,4,8 and device Part comparative example 1 carries out efficiency test in -10~80 DEG C of sections, and acquired results are as shown in 6 Fig. 2 of table.
Table 6
From the data of 6 Fig. 2 of table it is found that device 1,4,8 is material of the present invention and device architecture and device that known materials are arranged in pairs or groups Part comparative example 1 is compared, and not only Efficiency at Low Temperature is high, but also in temperature elevation process, efficiency is steadily increased.
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 (14)

1. a kind of using spiro fluorene as the compound of core, which is characterized in that shown in the structure of the compound such as general formula (1):
Wherein, R1For electron-withdrawing group, it is expressed as pyridyl group, quinolyl, isoquinolyl, phenanthroline base, benzimidazolyl, benzo One of oxazolyl, pyrido indyl, quinoxalinyl, triazine radical, alternatively, one or more H atoms in above-mentioned group It can be by D, F, C1-10Linear or branched alkyl group, C6-20Aryl, C5-20Heteroaryl replaces；
R2For electron-donating group, it is expressed as structure shown in general formula (2), general formula (3) or general formula (4):
Wherein, Ar1It is expressed as singly-bound, substituted or unsubstituted C6-30Arlydene, containing one or more heteroatomic substitutions or not 5~30 yuan of heteroarylidenes replaced；The hetero atom is N, O or S；
R3、R4Separately it is expressed as substituted or unsubstituted C6-60Aryl, substituted or unsubstituted 5-60 unit's heteroaryl；Institute Stating hetero atom is N, O or S；
R5、R6Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 unit's heteroaryl；Institute Stating hetero atom is N, O or S；R5、R6With substituent group or simultaneously loop type is connected with phenyl ring；
X is expressed as singly-bound, O, S or ethenylidene；
X1 is expressed as the imido grpup that the methylene that O, S, Se, alkyl-substituted methylene, aryl replace or aryl replace.
2. according to claim 1 using spiro fluorene as the compound of core, which is characterized in that R1It is expressed as in structural formula It is any:
3. according to claim 1 using spiro fluorene as the compound of core, which is characterized in that R2It is expressed as in structural formula It is any:
4. according to claim 1 using spiro fluorene as the compound of core, which is characterized in that the specific knot of the general formula (1) Structure formula is following any:
5. a kind of according to any one of claims 1-4 using spiro fluorene as the preparation method of the compound of core, which is characterized in that Include the following steps:
Step 1: synthetic intermediate II
By raw material I and boronic acid compounds R1-B(OH)2It is dissolved with toluene, Pd (PPh is added3)4And sodium carbonate, under an inert atmosphere, By above-mentioned mixed solution in 95~110 DEG C, react 10~24 hours, cooled to room temperature, and filtering reacting solution, filtrate into Row vacuum rotary steam crosses neutral silica gel column, obtains intermediate II；
The reaction equation occurred in step 1 is as follows:
Step 2: synthesising target compound
By intermediate II and R2- H is dissolved with toluene；Add Pd2(dba)3, tri-tert-butylphosphine, sodium tert-butoxide；In inert atmosphere Under, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 95-110 DEG C, cooling and filtering reacting solution, filtrate rotation It steams, crosses silicagel column, obtain target compound；
The reaction equation occurred in step 2 is as follows:
6. preparation method according to claim 5, which is characterized in that in step 1, the toluene dosage is every 1g raw material I It is dissolved with 30-50mL toluene；The molar ratio of the raw material I and boronic acid compounds is 1:(1.0~1.5)；Pd (the PPh3)4With The molar ratio of raw material I is (0.005~0.01): 1, the molar ratio of the sodium carbonate and raw material I is (1.5~3.0): 1；Step 2 In, the intermediate II and R2The molar ratio of-H is 1:(1.0~1.5), Pd2(dba)3Molar ratio with intermediate II is (0.006~0.02): 1, the molar ratio of tri-tert-butylphosphine and intermediate II is (0.006~0.02): 1, sodium tert-butoxide and intermediate The molar ratio of body II is (2.0~3.0): 1.
7. it is a kind of it is according to any one of claims 1-4 using spiro fluorene be the compound of core in organic electroluminescence device Using.
8. a kind of organic electroluminescence device, comprising: first electrode, second electrode and be set to the first electrode and second At least one layer of organic film between electrode, which is characterized in that it is any that the organic film material therefor contains claim 1-4 Using spiro fluorene as the compound of core described in item.
9. organic electroluminescence device according to claim 8, which is characterized in that the organic film includes hole transport Layer, luminescent layer and the electronic barrier layer being set between hole transmission layer and luminescent layer, the electronic barrier layer material therefor It is described in any item using spiro fluorene as the compound of core containing claim 1-4.
10. organic electroluminescence device according to claim 9, which is characterized in that the luminescent layer by material of main part and Dopant material constitute, the material of main part of the luminescent layer, the luminescent layer dopant material and the electronic barrier layer used in Meet following relationship between material:
A) Shu HOMOElectronic barrier layer-HOMOLuminescent layer material of main partShu≤0.4eV；
B) Shu LUMOElectronic barrier layer-LUMOLuminescent layer material of main partShu >=0.2eV；
C) Shu LUMOElectronic barrier layer-LUMOLuminescent layer dopant materialShu >=0.2eV；
d)T1 electronic barrier layer≥2.6eV。
11. organic electroluminescence device according to claim 9, which is characterized in that the hole transmission layer material therefor Structural formula such as general formula (5) shown in:
Wherein, D1、D2、D3Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3-50 member are miscellaneous Cyclophane base.
12. organic electroluminescence device according to claim 9, which is characterized in that the organic film further includes electronics Transport layer and hole injection layer, the hole transmission layer, electronic barrier layer and luminescent layer are set in turn in electron transfer layer and sky Between the implanted layer of cave, the structural formula of the electron transfer layer material therefor is any one of general formula (6)-(10):
Wherein, E1-E10Separately it is expressed as C1-30Alkyl, the C of linear or branched alkyl group substitution1-30Linear or branched alkyl group Substituted alkoxy, substituted or unsubstituted C6-40Aryl, substituted or unsubstituted 3-30 circle heterocyclic ring aryl, alternatively, E1-E10Point It is not expressed as H and E independently1-E10It is not simultaneously H.
13. organic electroluminescence device according to claim 12, which is characterized in that the hole injection layer material therefor Structural formula be any one of general formula (11), (12) or (13):
Wherein, F1-F3Separately it is expressed as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3-30 member heteroaryl Base；
G1-G6Separately it is expressed as itrile group, halogen atom, amide groups, alkoxy, ester group, nitro, C1-30Linear chain or branched chain alkane Carbon atom, the substituted or unsubstituted C of base substitution6-30Aryl, 3-30 circle heterocyclic ring aryl, alternatively, G1-G6Separately indicate It for H and is not simultaneously H.
14. a kind of display original set, which is characterized in that contain the described in any item organic electroluminescence devices of claim 8-13.
CN201810210418.3A 2018-03-14 2018-03-14 It is a kind of using spiro fluorene as the compound of core, preparation method and its application in organic electroluminescence device Pending CN110272380A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112321516A (en) * 2019-10-30 2021-02-05 广东聚华印刷显示技术有限公司 Organic compound and organic light emitting diode comprising same
WO2021206504A1 (en) * 2020-04-09 2021-10-14 주식회사 엘지화학 Organic light-emitting device
KR20210125939A (en) * 2020-04-09 2021-10-19 주식회사 엘지화학 Organic light emitting device
CN116730799A (en) * 2023-05-26 2023-09-12 西安欧得光电材料有限公司 OLED compound containing spirofluorene structure and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112321516A (en) * 2019-10-30 2021-02-05 广东聚华印刷显示技术有限公司 Organic compound and organic light emitting diode comprising same
CN112321516B (en) * 2019-10-30 2022-11-15 广东聚华印刷显示技术有限公司 Organic compound and organic light emitting diode comprising same
WO2021206504A1 (en) * 2020-04-09 2021-10-14 주식회사 엘지화학 Organic light-emitting device
KR20210125939A (en) * 2020-04-09 2021-10-19 주식회사 엘지화학 Organic light emitting device
CN114144901A (en) * 2020-04-09 2022-03-04 株式会社Lg化学 Organic light emitting device
KR102573176B1 (en) 2020-04-09 2023-09-04 주식회사 엘지화학 Organic light emitting device
CN116730799A (en) * 2023-05-26 2023-09-12 西安欧得光电材料有限公司 OLED compound containing spirofluorene structure and preparation method thereof
CN116730799B (en) * 2023-05-26 2024-01-12 西安欧得光电材料有限公司 OLED compound containing spirofluorene structure and preparation method thereof

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