CN107778220A - Compound and application in an organic light emitting device using fluorenes and nitrogenous hexa-member heterocycle as core - Google Patents

Compound and application in an organic light emitting device using fluorenes and nitrogenous hexa-member heterocycle as core Download PDF

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CN107778220A
CN107778220A CN201610799636.6A CN201610799636A CN107778220A CN 107778220 A CN107778220 A CN 107778220A CN 201610799636 A CN201610799636 A CN 201610799636A CN 107778220 A CN107778220 A CN 107778220A
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layer
compound
formula
hole
fluorenes
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张兆超
李崇
唐丹丹
张小庆
叶中华
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Priority to CN201610799636.6A priority Critical patent/CN107778220A/en
Priority to PCT/CN2017/099587 priority patent/WO2018041123A1/en
Publication of CN107778220A publication Critical patent/CN107778220A/en
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Abstract

The present invention relates to a kind of using fluorenes and nitrogenous hexa-member heterocycle as the compound of core, there should be following general structure (1)：Formula (1), in formula (1), R1、R2、R3One kind respectively in phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, isoquinolyl, phenanthroline base, benzimidazolyl, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base；In formula (1), Ar is expressed as one kind in phenyl, xenyl, naphthyl or pyridine radicals；In formula (1),It is expressed as nitrogenous hexa-member heterocycle, n=1,2 or 3.The present invention is using fluorenes and nitrogenous hexa-member heterocycle as skeleton, connected by aromatic group, nitrogenous hexa-member heterocycle therein is strong electro group, pass through the modification of fluorenes or aromatic group, HOMO energy levels are made freely to adjust, use as electron type luminescent material or used as hole barrier/electron transport layer materials, the photoelectric properties and service life of device can be improved.

Description

Compound and in an organic light emitting device using fluorenes and nitrogenous hexa-member heterocycle as core Using
Technical field
The present invention relates to a kind of using fluorenes and nitrogenous hexa-member heterocycle as the compound of core and answering in an organic light emitting device With belonging to technical field of semiconductors.
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 just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED luminescent devices together. As current device, when the two end electrodes to OLED luminescent devices apply voltage, 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, 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, use The performances such as life-span also need to further be lifted.
Proposing high performance research for OLED luminescent devices includes：The driving voltage of device is reduced, improves the luminous of device Efficiency, improve service life of device etc..In order to realize the continuous lifting of the performance of OLED, not only need from OLED The innovation of structure and manufacture craft, with greater need for the constantly research and innovation of oled light sulfate ferroelectric functional material, formulate out higher performance OLED Functional material.
Oled light sulfate ferroelectric functional material applied to OLED can be divided into two major classes, i.e. electric charge injection transmission from purposes Material and luminescent material, further, it 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 devices, it is desirable to various organic functional materials possess good photoelectric characteristic, 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 requires that material 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 passed including hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED is noted including at least hole Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and more The characteristics of sample.In addition, for the OLED collocation of different structure, used photoelectric functional material has stronger Selectivity, performance of the identical material in different structure device, it is also possible to completely totally different.
Therefore, for the difference in functionality film layer of the industry application requirement of current OLED, and OLED, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, and has high performance OLED functional materials or combination of materials, could realize device The overall characteristic of high 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
The technical problems to be solved by the invention be to provide it is a kind of using fluorenes and nitrogenous hexa-member heterocycle as the compound of core and Its application on organic electroluminescence device.The compound contain it is fluorene structured, have higher glass transition temperature and molecule heat Stability, suitable HOMO and lumo energy, higher Eg, is optimized by device architecture, can effectively lift the photoelectricity of OLED The life-span of performance and OLED.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of change using fluorenes and nitrogenous hexa-member heterocycle as core Compound, the compound have following general structure (1)：
In the formula (1), R1、R2、R3Respectively phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, isoquinolyl, phenanthrene One kind in sieve quinoline base, benzimidazolyl, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base；
In formula (1), Ar is expressed as one kind in phenyl, xenyl, naphthyl or pyridine radicals；
In formula (1),It is expressed as nitrogenous hexa-member heterocycle, n=1,2 or 3.
The beneficial effects of the invention are as follows：Using fluorenes and nitrogenous hexa-member heterocycle as skeleton, connected by aromatic group, it is therein Nitrogenous hexa-member heterocycle is strong electro group, by the modification of fluorenes or aromatic group, HOMO energy levels is freely adjusted, as electronics Type luminescent material is used or used as hole barrier/electron transport layer materials, can improve photoelectric properties and the use of device Life-span.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
A kind of compound using fluorenes and nitrogenous hexa-member heterocycle as core as described above of the invention, further, in formula (1)
Represented for formula (2), formula (3), formula (4), formula (5) or formula (6)：
Wherein, R2、R3Independently be expressed as R2、R3Respectively phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, different One kind in quinolyl, phenanthroline base, benzimidazolyl, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base.
A kind of compound using fluorenes and nitrogenous hexa-member heterocycle as core as described above of the invention, further, in formula (1)
It is expressed as：
Any of.
A kind of compound using fluorenes and nitrogenous hexa-member heterocycle as core as described above of the invention, further, the compound Concrete structure formula be：
Any of.
A kind of compound using fluorenes and nitrogenous hexa-member heterocycle as core as described above of the invention, further, the preparation method In reaction equation be：
Wherein, R1、R2、R3Respectively phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, isoquinolyl, phenanthroline base, benzene And one kind in imidazole radicals, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base；
Using Br-Ar-Br as raw material, by grignard reaction, RMgBr is made in the preparation method, then anti-with 9-Fluorenone Should, generate the tertiary alcohol；The subsequent tertiary alcohol and H-R1Reacted by friedel-craft, a bromo compound, Ran Houhe is madePass through The compound is made in C-C couplings.
Above-mentioned preparation method specifically comprises the following steps：
1) Br-Ar-Br and magnesium powder are raw material, and the Br-Ar-Br and magnesium powder molar ratio are 1:1, tetrahydrofuran is added, Under nitrogen atmosphere, 70 DEG C are heated to, back flow reaction 3-5 hours, no magnesium powder is remaining, and reaction is complete, generates grignard reagent；Above-mentioned The dosage of the tetrahydrofuran is preferably that 1gBr-Ar-Br adds 3-6ml tetrahydrofurans,
2) weigh 9-Fluorenone to be dissolved in tetrahydrofuran, the 9-Fluorenone and the Br-Ar-Br mol ratios are 1:1, then drip The grignard reagent for adding step 1) to prepare, after completion of dropwise addition, 60-70 DEG C is heated to, back flow reaction 10-25 hours, generation is a large amount of white The form salt precipitation of color, reaction terminate, and saturation NHCl is then added dropwise4Solution, the form salt is converted into the tertiary alcohol；Ether is used again Extraction obtains extract, the extract anhydrous sodium sulfate drying, then rotates desolventizing to without cut, obtains the tertiary alcohol and slightly produce Thing, gained tertiary alcohol crude product petroleum ether：Dichloromethane mixed solvent crosses neutral silica gel post, obtains solid tertiary alcohol purified product； Preferably above-mentioned petroleum ether：The volume ratio 3 of dichloromethane:2；The dosage of the tetrahydrofuran in step 2) is preferably every 1g9- Fluorenones are dissolved in 4-8ml tetrahydrofurans；The dosage of the ether is that the 1g tertiary alcohols are added in 5-10ml ether.
3) 1 is pressed:2 equivalents weigh solid tertiary alcohol purified product and R1-H, are dissolved in dichloromethane, the use of the dichloromethane Measure and be dissolved in for 1g solid tertiary alcohol purified products in 5-8ml dichloromethane, BFEE complexing is added dropwise under room temperature condition again Thing, the solid tertiary alcohol purified product are 1 with boron trifluoride etherate molar ratio:1.5,30-60 minutes are reacted, so Ethanol and water quenching are added afterwards to go out reaction, are then extracted with dichloromethane, anhydrous sodium sulfate drying, are rotated desolventizing to cut, stone Oily ether crosses neutral silica gel post, ethanol：Dichloromethane mixed solvent recrystallizes, and obtains a bromo compound；Preferably, the ethanol： Dichloromethane in the mixed solvent ethanol and methylene chloride volume ratio 1:1.
4) with a bromo compound and boronic acid compoundsIt is for raw material, toluene dissolving, the toluene dosage The bromo compounds of 1g mono- use 30-50ml toluene, wherein, a bromo compound and boronic acid compounds's Mol ratio is 1:(1.2~1.5)；
5) Pd (PPh are added into the final reaction system of step 4)3)4And sodium carbonate；
Wherein it is preferred to Pd (the PPh3)4Mol ratio with a bromo compound is (0.005~0.02):1, it is described The mol ratio of sodium carbonate and a bromo compound is (1.5~3.0):1；
6) mixed solution that under nitrogen protection, step 5) is obtained reacts 10~24 hours in 95~110 DEG C, natural It is cooled to room temperature, and filtering reacting solution, filtrate is rotated to solvent-free, is crossed neutral silica gel post, is obtained target product.
A kind of above-mentioned compound application in an organic light emitting device using fluorenes and nitrogenous hexa-member heterocycle as core of the present invention.
The present invention provides a kind of organic electroluminescence device, and the organic electroluminescence device includes at least one layer of functional layer Contain the above-mentioned compound containing dibenzo hexatomic ring and nitrogenous hexa-member heterocycle.
The present invention provides a kind of organic luminescent device, including hole barrier/electric transmission is layer by layer, the hole barrier/electricity Sub- transport layer is the above-mentioned compound using fluorenes and nitrogenous hexa-member heterocycle as core.
A kind of organic luminescent device as described above of the invention, further, in addition to transparent substrate layer, ito anode layer, hole Implanted layer, hole transport/electronic barrier layer, luminescent layer, electron injecting layer and negative electrode reflection electrode layer, the transparent substrate layer, Ito anode layer, hole injection layer, hole transport/electronic barrier layer, luminescent layer, hole barrier/electron transfer layer, electron injection Layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.
A kind of organic luminescent device as described above of the invention, further, the ito anode thickness degree is 130-150nm； Or/and the hole injection layer is material HAT-CN, thickness 10nm；Or/and hole transport/the electronic barrier layer passes for cave Defeated material NPB, thickness 80nm, or/and the luminescent layer, using CBP as material of main part, Ir (ppy) is as phosphorescence doping material Material, doping mass ratio is 10%, thickness 30nm, or/and the thickness of the hole barrier/electron transfer layer is 40nm, and/or The electron injecting layer for LiF materials, its thickness is 1nm, and/or the negative electrode reflection electrode layer is materials A l, its thickness For 100nm.
A kind of organic luminescent device, including luminescent layer as described above of the invention, the luminescent layer are with fluorenes and to be contained with above-mentioned Nitrogen hexa-member heterocycle is the compound of core and compound GHN is material of main part, and dopant material is Ir (ppy)3, it is described with fluorenes and to contain Nitrogen hexa-member heterocycle is the compound of core, compound GHN and Ir (ppy)3Blending mass ratio be 60:30:10, wherein, it is described Compound GHN structural formula is
A kind of organic luminescent device as described above of the invention, further, in addition to transparent substrate layer, ito anode layer, hole Implanted layer, hole transport/electronic barrier layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflection electricity Pole layer, the transparent substrate layer, ito anode layer, hole injection layer, hole transport/electronic barrier layer, luminescent layer, hole barrier/ Electron transfer layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.
A kind of organic luminescent device as described above of the invention, further, in addition to transparent substrate layer, ito anode layer, hole Implanted layer, hole transport/electronic barrier layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflection electricity Pole layer, the transparent substrate layer, ito anode layer, hole injection layer, hole transport/electronic barrier layer, luminescent layer, hole barrier/ Electron transfer layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.Above-mentioned preferably described ITO layer It is 130-150nm for anode layer thickness；Or/and the hole injection layer is material HAT-CN, thickness 10nm；It is or/and described Hole transport/electronic barrier layer is hole transport materials NPB, thickness 80nm, or/and the light emitting layer thickness is 30nm, or/and Hole barrier/the electron transport layer materials are TPBI, and its thickness is 40nm, and/or the electron injecting layer for LiF materials Material, its thickness is 1nm, and/or the negative electrode reflection electrode layer is materials A l, and its thickness is 100nm.
The present invention provides a kind of preparation method of organic luminescent device, comprises the following steps：
Ito anode layer on step a) cleaning transparent substrate layers；
Step b) is deposited hole injection layer material HAT-CN on ito anode layer, by vacuum evaporation mode and is used as hole Implanted layer；
Step c) is deposited hole mobile material NPB on hole injection layer, by vacuum evaporation mode and is used as hole transport Layer/electronic barrier layer；
Luminescent layer is deposited in step d) on hole transport/electronic barrier layer, and the luminescent layer is used as main body material using CBP Material, Ir (ppy) are used as phosphorescence dopant material；
Step e) is hindered on luminescent layer using the above-mentioned compound using fluorenes and nitrogenous hexa-member heterocycle as core as hole Barrier/electron transport layer materials；
Step f) is on hole barrier/electron transfer layer, vacuum evaporation electron injecting layer LiF；
Step g) is on electron injecting layer, and vacuum evaporation negative electrode Al is as negative electrode reflection electrode layer.
The compounds of this invention is connected using fluorenes and nitrogenous hexa-member heterocycle as skeleton by aromatic group, therein nitrogenous hexa-atomic Heterocycle is strong electro group, by the modification of fluorenes or aromatic group, HOMO energy levels is freely adjusted, and electron type can be used as to send out Luminescent material uses, and can also be used as hole barrier/electron transport layer materials.And 9 due to fluorenes introduce different groups, break Bad element's symmetry, avoids intermolecular aggtegation, and in molecular structure, each group rigidity is stronger, has high vitrifying temperature Degree and heat endurance, when the compounds of this invention is applied to OLED, can keep the membranous layer stability after material filming, improve OLED service life.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transport/electronic barrier layer, 5 be luminescent layer, and 6 be hole barrier/electron transfer layer, and 7 be electron injecting layer, and 8 be negative electrode reflection electrode layer.
Embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Embodiment 1
The synthesis of raw material A 1：
Synthetic route is as follows：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, add 15.6g 3, bromo- 1, the 1'- biphenyl of 4'- bis- (0.05mol) and 1.33gMg powder (0.05mol), 60ml tetrahydrofurans, 70 DEG C are heated to, back flow reaction 4 hours, no magnesium powder remains Remaining, reaction is complete, generates grignard reagent；
9.01g 9-Fluorenones (0.05mol) are dissolved in 50ml tetrahydrofurans, and above-mentioned grignard reagent is added dropwise, and 60 DEG C of reactions 24 are small When, a large amount of white precipitates are generated, are eventually adding saturation NHCl4Form salt is converted into alcohol；After completion of the reaction, ether extracts, and does Dry revolving, petroleum ether：Dichloromethane mixed solvent (3:2) silicagel column purifies, and obtaining the solid tertiary alcohol of yellowish, (yield is 91%)；The compound, molecular formula C are identified using DEI-MS25H17BrO, detected value [M+1]+=413.02, calculated value 412.05；
By 1:2 when measuring the above-mentioned tertiary alcohols of 16.5g (0.04mol) and 6.24g benzene (0.08mol) is dissolved in 100ml dichloromethane In, 8ml boron trifluoride etherates are added dropwise at ambient temperature, react 30 minutes, add 20ml ethanol and 20ml water quenchings Go out reaction, extracted with dichloromethane (20ml*3), dry revolving, the purifying of petroleum ether silicagel column, use ethanol：Dichloromethane is tied again Crystalline substance, yield 72%；The compound, molecular formula C are identified using DEI-MS31H21Br, detected value [M+1]+=473.04, calculate Value 472.08.
Embodiment 2
The synthesis of raw material A 2：
Synthetic route：
By the synthetic method preparing raw material A2 of the raw material A 1 in embodiment 1, difference is to replace 3 with Isosorbide-5-Nitrae-dibromobenzene, Bromo- 1, the 1'- biphenyl of 4'- bis-, benzene is replaced with biphenyl in three-step reaction；
The compound, molecular formula C are identified using DEI-MS31H21Br, detected value [M+1]+=473.06, calculated value 472.08。
Embodiment 3
The synthesis of raw material A 3：
Synthetic route：
By the synthetic method preparing raw material A3 of the raw material A 1 in embodiment 1, difference is to replace 3 with Isosorbide-5-Nitrae-dibromobenzene, The bromo- 1,1'- biphenyl of 4'- bis-；
The compound, molecular formula C are identified using DEI-MS25H17Br, detected value [M+1]+=397.11, calculated value 396.05。
Embodiment 4
The synthesis of raw material A 4：
Synthetic route：
By the synthetic method preparing raw material A4 of the raw material A 1 in embodiment 1, biphenyl is being used in difference in three-step reaction Instead of benzene；
The compound, molecular formula C are identified using DEI-MS37H25Br, detected value [M+1]+=549.08, calculated value 548.11。
Embodiment 5
The synthesis of raw material A 5：
Synthetic route：
By the synthetic method preparing raw material A5 of the raw material A 1 in embodiment 1, difference is to be joined with 4,4'-, bis- bromo- 1,1'- Benzene replaces the bromo- 1,1'- biphenyl of 3,4'- bis-；
The compound, molecular formula C are identified using DEI-MS31H21Br, detected value [M+1]+=473.15, calculated value 472.08。
Embodiment 6
The synthesis of raw material A 6：
Synthetic route：
By the synthetic method preparing raw material A2 of the raw material A 1 in embodiment 1, difference is to replace 3 with Isosorbide-5-Nitrae-dibromobenzene, Bromo- 1, the 1'- biphenyl of 4'- bis-, benzene is replaced with pyridine in three-step reaction；
The compound, molecular formula C are identified using DEI-MS24H16BrN, detected value [M+1]+=397.98, calculated value 397.05。
The synthesis of the compound 3 of embodiment 7：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 3,0.012mol raw material B1 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.4%, yield 77.5%.
Elementary analysis structure (molecular formula C40H27N3)：Theoretical value C, 87.40；H,4.95；N,7.64；Test value：C, 87.41；H,4.95；N,7.63.
HPLC-MS：Material molecule amount is 549.22, surveys molecular weight 549.45.
The synthesis of the compound 4 of embodiment 8：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 3,0.012mol raw material B2 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.5%, yield 79.2%.
Elementary analysis structure (molecular formula C41H28N2)：Theoretical value C, 89.75；H,5.14；N,5.11；Test value：C, 89.76；H,5.12；N,5.12.
HPLC-MS：Material molecule amount is 548.23, surveys molecular weight 548.49.
The synthesis of the compound 5 of embodiment 9：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 1,0.012mol raw material B3 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.3%, yield 78.1%.
Elementary analysis structure (molecular formula C48H33N)：Theoretical value C, 92.42；H,5.33；N,2.25；Test value：C, 92.40；H,5.34；N,2.26.
HPLC-MS：Material molecule amount is 623.26, surveys molecular weight 623.51.
The synthesis of the compound 7 of embodiment 10：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 2,0.012mol raw material B3 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.5%, yield 74.3%.
Elementary analysis structure (molecular formula C48H33N)：Theoretical value C, 92.42；H,5.33；N,2.25；Test value：C, 92.43；H,5.32；N,2.25.
HPLC-MS：Material molecule amount is 623.26, surveys molecular weight 623.53.
The synthesis of the compound 13 of embodiment 11：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 3,0.012mol raw material B4 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.7%, yield 78.9%.
Elementary analysis structure (molecular formula C42H29N)：Theoretical value C, 92.11；H,5.34；N,2.56；Test value：C, 92.10；H,5.35；N,2.55.
HPLC-MS：Material molecule amount is 547.23, surveys molecular weight 547.49.
The synthesis of the compound 15 of embodiment 12：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 3,0.012mol raw material B5 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.2%, yield 77.8%.
Elementary analysis structure (molecular formula C40H27N3)：Theoretical value C, 87.40；H,4.95；N,7.64；Test value：C, 87.41；H,4.965；N,7.63.
HPLC-MS：Material molecule amount is 549.22, surveys molecular weight 549.47.
The synthesis of the compound 26 of embodiment 13：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 3,0.012mol raw material C1 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.6%, yield 77.3%.
Elementary analysis structure (molecular formula C39H26N4)：Theoretical value C, 85.07；H,4.76；N,10.17；Test value：C, 85.06；H,4.78；N,10.16.
HPLC-MS：Material molecule amount is 550.22, surveys molecular weight 550.43.
The synthesis of the compound 28 of embodiment 14：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 4,0.012mol raw material C2 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.1%, yield 65.1%.
Elementary analysis structure (molecular formula C53H36N2)：Theoretical value C, 90.83；H,5.18；N,4.00；Test value：C, 90.81；H,5.17；N,4.02.
HPLC-MS：Material molecule amount is 700.29, surveys molecular weight 700.55.
The synthesis of the compound 35 of embodiment 15：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 5,0.012mol raw material C1 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.4%, yield 71.7%.
Elementary analysis structure (molecular formula C45H30N4)：Theoretical value C, 86.24；H,4.82；N,8.94；Test value：C, 86.22；H,4.83；N,8.95.
HPLC-MS：Material molecule amount is 626.25, surveys molecular weight 626.52.
The synthesis of the compound 40 of embodiment 16：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 9, difference is to replace raw material B3 with raw material C3；
Elementary analysis structure (molecular formula C47H32N2)：Theoretical value C, 90.35；H,5.16；N,4.48；Test value：C, 90.38；H,5.15；N,4.47.
HPLC-MS：Material molecule amount is 624.26, surveys molecular weight 625.54.
The synthesis of the compound 42 of embodiment 17：
Synthetic route：
Prepared by the synthetic method of compound 7 in embodiment 10, difference is to replace raw material B3 with raw material C3；
Elementary analysis structure (molecular formula C47H32N2)：Theoretical value C, 90.35；H,5.16；N,4.48；Test value：C, 90.36；H,5.17；N,4.47.
HPLC-MS：Material molecule amount is 624.26, surveys molecular weight 624.53.
The synthesis of the compound 44 of embodiment 18：
Synthetic route：
Prepared by the synthetic method of compound 3 in embodiment 7, difference is to replace raw material B1 with raw material C4；
Elementary analysis structure (molecular formula C47H32N2)：Theoretical value C, 90.35；H,5.16；N,4.48；Test value：C, 90.37；H,5.15；N,4.48.
HPLC-MS：Material molecule amount is 624.26, surveys molecular weight 624.57.
The synthesis of the compound 47 of embodiment 19：
Synthetic route：
Prepared by the synthetic method of compound 3 in embodiment 7, difference is to replace raw material B1 with raw material D1；
Elementary analysis structure (molecular formula C40H27N3)：Theoretical value C, 87.40；H,4.95；N,7.64；Test value：C, 87.40；H,4.95；N,7.65.
HPLC-MS：Material molecule amount is 549.22, surveys molecular weight 549.45.
The synthesis of the compound 51 of embodiment 20：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 9, difference is to replace raw material B3 with raw material D1；
Elementary analysis structure (molecular formula C46H31N3)：Theoretical value C, 88.29；H,4.99；N,6.72；Test value：C, 88.30；H,5.00；N,6.70.
HPLC-MS：Material molecule amount is 625.25, surveys molecular weight 625.56.
The synthesis of the compound 53 of embodiment 21：
Synthetic route：
Prepared by the synthetic method of compound 7 in embodiment 10, difference is to replace raw material B3 with raw material D1；
Elementary analysis structure (molecular formula C46H31N3)：Theoretical value C, 88.29；H,4.99；N,6.72；Test value：C, 88.27；H,5.00；N,6.73.
HPLC-MS：Material molecule amount is 625.25, surveys molecular weight 625.59.
The synthesis of the compound 58 of embodiment 22：
Synthetic route：
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, 0.01mol raw material A 6,0.012mol raw material D1 are added, 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, 150ml toluene, it is heated to 105 DEG C and flows back 24 hours, sample point plate, show Show that no bromo-derivative is remaining, reaction is complete；Natural cooling, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target Product, purity 99.4%, yield 71.7%.
Elementary analysis structure (molecular formula C39H26N4)：Theoretical value C, 85.07；H,4.76；N,10.17；Test value：C, 85.07；H,4.75；N,10.18.
HPLC-MS：Material molecule amount is 550.22, surveys molecular weight 550.47.
Hereinafter, compound provided by the present invention is described in detail by device embodiments 1-10 and device comparative example 1 to be used as Hole barrier or electron transport layer materials and emitting layer material, are applied on electroluminescent device, and prove it with comparative example 1 Beneficial effect.The performance test results of each embodiment obtained device are as shown in table 1.
Device embodiments 1
A kind of electroluminescent device, its preparation process include：
A) the ito anode layer 2 cleaned on transparent substrate layer 1, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively Minute, then handled 2 minutes in plasma cleaner；
B) on ito anode layer 2, hole injection layer material HAT-CN, thickness 10nm are deposited by vacuum evaporation mode, This layer is as hole injection layer 3；
C) on hole injection layer 3, hole mobile material NPB, thickness 80nm, the layer are deposited by vacuum evaporation mode For hole transmission layer or electronic barrier layer 4；
D) luminescent layer 5 is deposited on hole transport or electronic barrier layer 4, CBP is as material of main part, Ir (ppy)3As Phosphorescence dopant material, Ir (ppy)3Mass ratio with CBP is 1:9, thickness 30nm；
E) on luminescent layer 5, hole blocking layer or electron transport layer materials, thickness are used as using the compounds of this invention 3 For 40nm, this layer of organic material uses as hole barrier or electron transfer layer 6；
F) on hole barrier or electron transfer layer 6, vacuum evaporation electron injecting layer LiF, thickness 1nm, the layer is Electron injecting layer 7；
G) on electron injecting layer 7, vacuum evaporation negative electrode Al (100nm), the layer is negative electrode reflection electrode layer 8；
After the making that electroluminescent device is completed according to above-mentioned steps, the driving voltage of measurement device, current efficiency, it is tied Fruit is shown in Table 1.
The molecular machinery formula of associated materials is as follows：
Device embodiments 2
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into the compounds of this invention 4.The detection data of gained electroluminescent device are shown in Table 1.
Device embodiments 3
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into the compounds of this invention 15.The detection data of gained electroluminescent device are shown in Table 1.
Device embodiments 4
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into the compounds of this invention 26.The detection data of gained electroluminescent device are shown in Table 1.
Device embodiments 5
The difference of the present embodiment and device embodiments 1 is：Hole barrier/electron transfer layer of electroluminescent device 6 materials are changed into the compounds of this invention 35.The detection data of gained electroluminescent device are shown in Table 1.
Device embodiments 6
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into TPBI, and luminescent layer material of main part is changed into the compounds of this invention 5, and dopant material is Ir (ppy)3, chemical combination of the present invention Thing 5 and dopant material Ir (ppy)3Mass ratio be 9：1, the detection data of gained electroluminescent device are shown in Table 1.
Device embodiments 7
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into TPBI, and luminescent layer material of main part is changed into the compounds of this invention 42, and dopant material is Ir (ppy)3, the present inventionization Compound 42 and dopant material Ir (ppy)3Mass ratio be 9：1, the detection data of gained electroluminescent device are shown in Table 1.
Device embodiments 8
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into TPBI, and luminescent layer material of main part is changed into the compounds of this invention 51 and compound GHN, dopant material Ir (ppy)3, the compounds of this invention 51, compound GHN and dopant material are Ir (ppy)3Blending mass ratio be 60:30:10, gained The detection data of electroluminescent device are shown in Table 1.
Device embodiments 9
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into TPBI, and luminescent layer material of main part is changed into the compounds of this invention 53 and compound GHN, dopant material Ir (ppy)3, the compounds of this invention 53, compound GHN and dopant material are Ir (ppy)3The mass ratio of blending is 60:30:10, gained The detection data of electroluminescent device are shown in Table 1.
Device embodiments 10
The difference of the present embodiment and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into two layers, and wherein the compounds of this invention 58 uses separately as hole blocking layer, thickness 5nm, the following knot Structure compound A and compound B are according to mass ratio 1:1 ratio is mutually mixed to be used as electron transfer layer, and its thickness is 35nm. The detection data of gained electroluminescent device are shown in Table 1.
Device comparative example 1
The difference of this comparative example and device embodiments 1 is：The hole barrier or electric transmission of electroluminescent device 6 material of layer are changed into TPBI.The detection data of gained electroluminescent device are shown in Table 1.
Table 1
Numbering Current efficiency Color The LT95 life-spans
Device embodiments 1 1.3 Green glow 3.3
Device embodiments 2 1.2 Green glow 2.9
Device embodiments 3 1.4 Green glow 3.5
Device embodiments 4 1.3 Green glow 3.1
Device embodiments 5 1.4 Green glow 3.4
Device embodiments 6 1.5 Green glow 5.1
Device embodiments 7 1.4 Green glow 4.5
Device embodiments 8 1.7 Green glow 8.2
Device embodiments 9 1.6 Green glow 7.5
Device embodiments 10 1.5 Green glow 4.5
Device comparative example 1 1.0 Green glow 1.0
Note：For device detection performance using device comparative example 1 as reference, the device property indices of comparative example 1 are set to 1.0. The current efficiency of comparative example 1 is 28cd/A (@10mA/cm2)；CIE chromaticity coordinates is (0.33,0.63)；The LT95 longevity under 5000 brightness Life decays to 2.5Hr.
Above-mentioned hole blocking layer is also referred to as electron transfer layer.
It can be seen that the compounds of this invention can be applied to OLED luminescent devices and make by the result of table 1, and and comparative example Compare, either efficiency or life-span obtain the service life acquisition of larger change, particularly device than known OLED material Larger lifting.
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 (12)

1. a kind of compound using fluorenes and nitrogenous hexa-member heterocycle as core, it is characterised in that the compound has following structure Formula (1)：
In the formula (1), R1、R2、R3Independently be expressed as phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, isoquinoline One kind in quinoline base, phenanthroline base, benzimidazolyl, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base；
In formula (1), Ar is expressed as one kind in phenyl, xenyl, naphthyl or pyridine radicals；
In formula (1),It is expressed as nitrogenous hexa-member heterocycle, n=1,2 or 3.
A kind of 2. compound using fluorenes and nitrogenous hexa-member heterocycle as core according to claim 1, it is characterised in that formula (1) in
Represented for formula (2), formula (3), formula (4), formula (5) or formula (6)：
Wherein, R2、R3Independently be expressed as phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, isoquinolyl, phenanthroline One kind in base, benzimidazolyl, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base.
A kind of 3. compound using fluorenes and nitrogenous hexa-member heterocycle as core according to claim 1, it is characterised in that formula (1) in
It is expressed as：
Any of.
4. compound according to claim 1, it is characterised in that the concrete structure formula of the compound is：
Any of.
A kind of 5. preparation method of any one of Claims 1-4 compound, it is characterised in that the reaction in the preparation method Equation is：
Wherein, R1、R2、R3Respectively phenyl, xenyl, naphthyl, pyridine radicals, quinolyl, isoquinolyl, phenanthroline base, benzo miaow One kind in oxazolyl, benzoxazolyl, pyrido indyl, quinoxalinyl or naphthyridines base；
Ar is one kind in phenyl, xenyl, naphthyl or pyridine radicals；
For nitrogenous hexa-member heterocycle, n=1,2 or 3；
The preparation method by grignard reaction, is made RMgBr, then reacted with 9-Fluorenone using Br-Ar-Br as raw material, Generate the tertiary alcohol；The subsequent tertiary alcohol and H-R1Reacted by friedel-craft, a bromo compound, Ran Houhe is madePass through C-C The compound is made in coupling.
6. using fluorenes and nitrogenous hexa-member heterocycle it is the compound of core in organic illuminator described in a kind of any one of Claims 1-4 Application in part.
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 compound described in any one of Claims 1-4.
8. a kind of organic luminescent device, including hole barrier/electron transfer layer 6, it is characterised in that the hole barrier/electronics Transport layer is the compound using fluorenes and nitrogenous hexa-member heterocycle as core described in any one of Claims 1-4.
9. a kind of organic luminescent device according to claim 8, it is characterised in that also including transparent substrate layer, ito anode Layer, hole injection layer, hole transport/electronic barrier layer, luminescent layer, electron injecting layer and negative electrode reflection electrode layer are described transparent Substrate layer, ito anode layer, hole injection layer, hole transport/electronic barrier layer, luminescent layer, hole barrier/electron transfer layer, electricity Sub- implanted layer and negative electrode reflection electrode layer stacks gradually arrangement from bottom to up.
10. a kind of organic luminescent device according to claim 9, it is characterised in that the hole injection layer is material HAT- CN, thickness 10nm；Or/and hole transport/the electronic barrier layer is hole transport materials NPB, thickness 80nm, or/and institute Luminescent layer 5 is stated using CBP as material of main part, Ir (ppy)3As phosphorescence dopant material, doping mass ratio is 10%, and thickness is 30nm, or/and the thickness of the hole barrier/electron transfer layer is 40nm, and/or the electron injecting layer for LiF materials, Its thickness is 1nm, and/or the negative electrode reflection electrode layer is materials A l, and its thickness is 100nm.
11. a kind of organic luminescent device, including luminescent layer, it is characterised in that the luminescent layer is any with Claims 1-4 The compound and compound GHN using fluorenes and nitrogenous hexa-member heterocycle as core is material of main part, dopant material Ir (ppy)3, described in any one of Claims 1-4 using fluorenes and nitrogenous hexa-member heterocycle as the compound of core, compound GHN and Ir(ppy)3Blending mass ratio be 60:30:10, wherein, the structural formula of the compound GHN is
12. a kind of preparation method of organic luminescent device, it is characterised in that comprise the following steps：
Ito anode layer on step a) cleaning transparent substrate layers；
Step b) is deposited hole injection layer material HAT-CN on ito anode layer, by vacuum evaporation mode and is used as hole injection Layer；
Step c) is deposited hole mobile material NPB on hole injection layer, by vacuum evaporation mode and is used as hole transmission layer/electricity Sub- barrier layer；
Luminescent layer is deposited on hole transport/electronic barrier layer in step d), using CBP as material of main part, the conducts of Ir (ppy) 3 Phosphorescence dopant material；
For step e) on luminescent layer, usage right requires the change using fluorenes and nitrogenous hexa-member heterocycle as core described in 1 to 4 any one Compound is as hole blocking layer/electron transport layer materials；
Step f) is on hole barrier/electron transfer layer, vacuum evaporation electron injecting layer LiF；
Step g) is on electron injecting layer, and vacuum evaporation negative electrode Al is as negative electrode reflection electrode layer.
CN201610799636.6A 2016-08-31 2016-08-31 Compound and application in an organic light emitting device using fluorenes and nitrogenous hexa-member heterocycle as core Pending CN107778220A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111244306A (en) * 2018-11-29 2020-06-05 宇瑞(上海)化学有限公司 Top-emitting organic light-emitting diode unit
CN112409243A (en) * 2019-08-23 2021-02-26 支志明 Tetradentate ligand, gold (III) complex, and preparation method and application thereof
CN114746402A (en) * 2020-01-30 2022-07-12 东丽株式会社 Compound, organic thin-film light-emitting element, display device, and lighting device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116888111A (en) * 2021-01-29 2023-10-13 出光兴产株式会社 Compound, material for organic electroluminescent element, and electronic device
CN114276379A (en) * 2021-12-16 2022-04-05 西安凯翔光电科技有限公司 Organic light-emitting compound and organic electroluminescent device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100131745A (en) * 2009-06-08 2010-12-16 제일모직주식회사 Composition for organic photoelectric device and organic photoelectric device using the same
CN102421868A (en) * 2009-05-15 2012-04-18 第一毛织株式会社 Compound for organic photoelectric device and organic photoelectric device comprising same
CN106981576A (en) * 2015-12-22 2017-07-25 三星显示有限公司 Organic light emitting apparatus
CN107129471A (en) * 2016-02-26 2017-09-05 三星Sdi株式会社 Organic compound, organic photoelectric device and display device
CN107531650A (en) * 2015-08-21 2018-01-02 株式会社Lg化学 Compound and the organic electronic element for including it

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977006A (en) * 2012-12-21 2013-03-20 南京邮电大学 Pyridine-fluorene organic electrophosphorescence main body luminescent material and preparation method thereof
CN106478609B (en) * 2015-08-31 2019-03-26 上海和辉光电有限公司 A kind of material applied to the field OLED

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102421868A (en) * 2009-05-15 2012-04-18 第一毛织株式会社 Compound for organic photoelectric device and organic photoelectric device comprising same
KR20100131745A (en) * 2009-06-08 2010-12-16 제일모직주식회사 Composition for organic photoelectric device and organic photoelectric device using the same
CN107531650A (en) * 2015-08-21 2018-01-02 株式会社Lg化学 Compound and the organic electronic element for including it
CN106981576A (en) * 2015-12-22 2017-07-25 三星显示有限公司 Organic light emitting apparatus
CN107129471A (en) * 2016-02-26 2017-09-05 三星Sdi株式会社 Organic compound, organic photoelectric device and display device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111244306A (en) * 2018-11-29 2020-06-05 宇瑞(上海)化学有限公司 Top-emitting organic light-emitting diode unit
CN112409243A (en) * 2019-08-23 2021-02-26 支志明 Tetradentate ligand, gold (III) complex, and preparation method and application thereof
CN114746402A (en) * 2020-01-30 2022-07-12 东丽株式会社 Compound, organic thin-film light-emitting element, display device, and lighting device

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