CN109748899A - A kind of compound containing ketone and its application on organic electroluminescence device - Google Patents

A kind of compound containing ketone and its application on organic electroluminescence device Download PDF

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CN109748899A
CN109748899A CN201711071819.7A CN201711071819A CN109748899A CN 109748899 A CN109748899 A CN 109748899A CN 201711071819 A CN201711071819 A CN 201711071819A CN 109748899 A CN109748899 A CN 109748899A
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CN109748899B (en
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陈海峰
李崇
张兆超
张小庆
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
    • C07C49/755—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups a keto group being part of a condensed ring system with two or three rings, at least one ring being a six-membered aromatic ring
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    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
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    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
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    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07—ORGANIC CHEMISTRY
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Abstract

The invention discloses a kind of compound containing ketone and its applications on organic electroluminescence device, the compound is made of ketone and spiral shell anthracene fluorenes class group, with deep HOMO energy level and high electron mobility, it is suitable as hole barrier materials or electron transport material application；The present invention contains the structure of hole group, can balancing material electrons and holes so that material can be used as inclined electron type luminescent layer material of main part and use；In addition, the compounds of this invention group rigidity is stronger, have the characteristics that intermolecular be not easy to crystallize, be not easy to assemble, with good filming.After being applied to OLED device as organic electroluminescent functional layer material, the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.

Description

A kind of compound containing ketone and its application on organic electroluminescence device
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of compound containing ketone and its in Organic Electricity Application on electroluminescence device.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is very extensive.Structure of the OLED luminescent device like sandwich, including electrode material film layer, and it is clipped in different electricity Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together Optical device.As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer function Positive and negative charge in energy 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: to reduce the driving of device Voltage improves the luminous efficiency of device, improves the service life etc. of device.In order to realize that the continuous of performance of OLED device mentions It rises, not only needs the innovation from OLED device structure and manufacture craft, constantly study and create with greater need for oled light sulfate ferroelectric functional material Newly, the functional material of higher performance OLED is formulated out.Oled light sulfate ferroelectric functional material applied to OLED device can be drawn from purposes It is divided into two major classes, i.e. charge injection transmission material and luminescent material further can also inject charge into transmission material and be divided into electronics Transmission material, electron-blocking materials, hole injection transmission material and hole barrier materials are injected, luminescent material can also be divided into Main body luminescent material and dopant material.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 there is good carrier mobility, high-vitrification conversion Temperature etc., the material of main part as luminescent layer require 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 current OLED The industry application requirement of device and the different function film layer of OLED device, the photoelectric characteristic demand of device, it is necessary to which selection is more suitable It closes, OLED functional material or combination of materials with high performance, is just able to achieve the comprehensive of the high efficiency of device, long-life and low-voltage Close characteristic.For current OLED shows the actual demand of Lighting Industry, the development of OLED material is also far from enough at present, falls behind In the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of compound containing ketone and its organic Application on electroluminescent device.The compounds of this invention contains ketone structure, and glass transition temperature with higher and molecule heat are steady Qualitative, suitable HOMO and lumo energy, high electron mobility can effectively improve device after being applied to OLED device production The service life of luminous efficiency and OLED device.
Technical scheme is as follows: a kind of compound containing ketone, shown in the structure of the compound such as general formula (1):
In general formula (1), Ar2It is expressed as the C for being substituted or being unsubstituted1-10Alkyl, the C for replacing or being unsubstituted6-30Virtue Base, the C for being substituted or being unsubstituted5-30One of heteroaryl；
In general formula (1), Ar1、Ar3The C for being expressed as singly-bound, being substituted or being unsubstituted independently6-30Arlydene, warp The C for replacing or being unsubstituted5-30One of inferior heteroaryl；Ar1It is also denoted as the C for being substituted or being unsubstituted1-10Alkane Base, the C for being substituted or being unsubstituted6-30Aryl, the C for being substituted or being unsubstituted5-30One of heteroaryl；
In general formula (1), X is expressed as carbon atom, oxygen atom or sulphur atom；
When X is carbon atom, k=1, m, n independently be expressed as 0 or 1, and m, n be not identical；
When X is oxygen atom or sulphur atom, k=0, m=0, n=1.
In general formula (1), X1、X2Independently be expressed as singly-bound, oxygen atom, C1-10The Asia that linear or branched alkyl group replaces One of the imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl that alkyl, aryl replace replace；X1、X2At least one For singly-bound.
Based on the above technical solution, the present invention can also be improved as follows.
Further, shown in the structure of the compound such as general formula (2), general formula (3), general formula (4) or general formula (5):
Further, the Ar1、Ar3One be separately expressed as in singly-bound, phenylene, biphenylene or naphthylene Kind；Ar1It is also denoted as one of methyl, phenyl, xenyl or naphthalene；
Ar2It is expressed as one of methyl, phenyl, xenyl or naphthalene.
Further, in the general formula (1)It indicates are as follows:
One of.
Further, the concrete structure formula of the compound are as follows:
Any one of.
The present invention also provides a kind of preparation method of compound as described above, the reaction equation that occurs in preparation process Are as follows:
(1) when X is oxygen atom or sulphur atom, k=0, m=0, n=1:
Work as Ar3When not indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
Raw material A and intermediate M are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4With K2CO3, 95~110 DEG C of 10~24 hours of reaction under an inert atmosphere；After raw material fully reacting, cooling, filtering, by filtrate Revolving removes solvent, and crude product crosses silicagel column, obtains target compound；
Wherein, the dosage of the toluene and ethyl alcohol is that every gram of raw material A uses 30~50mL toluene and 5~10mL ethyl alcohol, The molar ratio of intermediate M and raw material A is (1~1.5): 1, Pd (PPh3)4Molar ratio with raw material A is (0.006~0.02): 1, K2CO3Molar ratio with raw material A is (1.5~2): 1；
Work as Ar3When indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
It under nitrogen atmosphere, weighs raw material A and is dissolved in tetrahydrofuran, then raw material B and tetrakis triphenylphosphine palladium are added, stir Mixture is mixed, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux at 70-90 DEG C of reaction temperature 5-20 hours；After reaction, cooling plus water, mixture are extracted with dichloromethane, and extract liquor is dried, filtered with anhydrous sodium sulfate And be concentrated under reduced pressure, gained residue crosses silica gel column purification, obtains target compound；
Wherein, the molar ratio of the raw material A and raw material B are 1:(1.0~1.5), tetrakis triphenylphosphine palladium and raw material A are rubbed You are than being (0.001~0.02): 1, the molar ratio of potassium carbonate and raw material A is (1.0~2.0): 1, THF and raw material A amount ratio For 1g:(10~30) ml.
(2) when X is carbon atom, k=1, m=0, n=1:
Work as Ar3When not indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
Raw material A and intermediate N are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4With K2CO3, 95~110 DEG C of 10~24 hours of reaction under an inert atmosphere；After raw material fully reacting, cooling, filtering, by filtrate Revolving removes solvent, and crude product crosses silicagel column, obtains target compound；
Wherein, the dosage of the toluene and ethyl alcohol is that every gram of raw material A uses 30~50mL toluene and 5~10mL ethyl alcohol, The molar ratio of intermediate N and raw material A is (1~1.5): 1, Pd (PPh3)4Molar ratio with raw material A is (0.006~0.02): 1, K2CO3Molar ratio with raw material A is (1.5~2): 1；
Work as Ar3When indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
It under nitrogen atmosphere, weighs raw material A and is dissolved in tetrahydrofuran, then raw material C and tetrakis triphenylphosphine palladium are added, stir Mixture is mixed, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux at 70-90 DEG C of reaction temperature 5-20 hours；After reaction, cooling plus water, mixture are extracted with dichloromethane, and extract liquor is dried, filtered with anhydrous sodium sulfate And be concentrated under reduced pressure, gained residue crosses silica gel column purification, obtains target compound；
Wherein, the molar ratio of the raw material A and raw material C are 1:(1.0~1.5), tetrakis triphenylphosphine palladium and raw material A are rubbed You are than being (0.001~0.02): 1, the molar ratio of potassium carbonate and raw material A is (1.0~2.0): 1, THF and raw material A amount ratio For 1g:(10~30) ml；
(3) when X is carbon atom, k=1, m=1, n=0:
Specific reaction process are as follows:
It under nitrogen atmosphere, weighs raw material A and is dissolved in tetrahydrofuran, then raw material D and tetrakis triphenylphosphine palladium are added, stir Mixture is mixed, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux at 70-90 DEG C of reaction temperature 5-20 hours；After reaction, cooling plus water, mixture are extracted with dichloromethane, and extract liquor is dried, filtered with anhydrous sodium sulfate And be concentrated under reduced pressure, gained residue crosses silica gel column purification, obtains target compound；
The molar ratio of the raw material A and raw material D are 1:1.0~1.5, and the molar ratio of tetrakis triphenylphosphine palladium and raw material A is The molar ratio of 0.001~0.02:1, potassium carbonate and raw material A is 1.0~2.0:1, the amount ratio of raw material A and THF be 1g:10~ 30ml。
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function Layer contains the above-mentioned compound containing ketone.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the organic electroluminescence device includes luminescent layer, and the luminescent layer contains the above-mentioned change containing ketone Close object.
Further, the organic electroluminescence device includes hole blocking layer/electron transfer layer, and the hole blocking layer/ Electron transfer layer contains the above-mentioned compound containing ketone.
It include organic electroluminescence device as described above the present invention also provides a kind of illumination or display element.
The present invention is beneficial to be had the technical effect that
The compounds of this invention is connected using ketone and spiral shell anthracene fluorenes class group as skeleton by singly-bound or aromatic group, ketone and spiral shell Anthracene fluorenes class group is electro group, has deep HOMO energy level and high electron mobility, passes through repairing for other aromatic groups Decorations, adjust HOMO energy level freely, can be used as the use of electron type luminescent material, can also be used as hole barrier or electron-transport Layer material uses.The present invention contains the structure of hole group, can balancing material electrons and holes so that material can be used as it is partially electric Subtype luminescent layer material of main part uses.
In addition, ketone and spiral shell anthracene fluorenes class group are all electron-withdrawing groups, the molecule of composition does not have symmetry, avoids intermolecular Aggtegation, the compounds of this invention group rigidity is stronger, has and intermolecular be not easy to crystallize, be not easy to assemble, with good filming Property the characteristics of, have high glass transition temperature and thermal stability, so, the compounds of this invention be applied to OLED device when, can protect Membranous layer stability after holding material filming improves OLED device service life.
After compound of the present invention is applied to OLED device as organic electroluminescent functional layer material, the electric current of device Efficiency, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly, in OLED There is good application effect in luminescent device, there is good industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transport or electronic blocking Layer, 5 be luminescent layer, and 6 be electron-transport or hole blocking layer, and 7 be electron injecting layer, and 8 be cathode reflection electrode layer.
Fig. 2 is current efficiency variation with temperature curve.
Specific embodiment
Embodiment 1: the synthesis of intermediate M:
(1) raw material B and raw material E are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4With K2CO3, 95~110 DEG C of 10~24 hours of reaction under an inert atmosphere；After raw material fully reacting, cooling, filtering, by filtrate Revolving removes solvent, and crude product crosses silicagel column, obtains target compound；
Wherein, the dosage of the toluene and ethyl alcohol is that every gram of raw material E uses 30~50mL toluene and 5~10mL ethyl alcohol, The molar ratio of raw material B and raw material E is (1~1.5): 1, Pd (PPh3)4Molar ratio with raw material E is (0.006~0.02): 1, K2CO3Molar ratio with raw material E is (1.5~2): 1.
(2) under nitrogen protection, it weighs intermediate S to be dissolved in tetrahydrofuran, is cooled to -78 DEG C, then to reaction system The middle tetrahydrofuran solution that 1.6mol/L n-BuLi is added, is added triisopropyl borate ester after reacting 3h at -78 DEG C, reacts Then reaction system is risen to 0 DEG C by 2h, 2mol/L hydrochloric acid solution is added, and stirs 3h, and ether extraction, extraction is added in fully reacting Anhydrous magnesium sulfate drying is added in liquid, and revolving is recrystallized with alcohol solvent, obtains intermediate M；
Wherein, the molar ratio of the intermediate S and n-BuLi is 1:(1~1.5)；The intermediate S and boric acid three are different The molar ratio of propyl ester is 1:(1~1.5).
By taking intermediate M-1 synthesis as an example:
(1) 0.01mol raw material E-2 and 0.012mol raw material B-1 is dissolved in the 150mL (V of toluene and ethyl alcoholToluene: VEthyl alcohol= 5:1) in mixed solution, 0.0002mol Pd (PPh is added after deoxygenation3)4With 0.02mol K2CO3, 110 DEG C under an inert atmosphere 24 hours are reacted, after raw material fully reacting, filtrate is rotated and removes solvent by cooling, filtering, and crude product is crossed silicagel column, obtained To intermediate target product S-2；Elemental analysis structure (molecular formula C19H11BrO2): theoretical value C, 64.98；H,3.16；Br, 22.75；Test value: C, 64.98；H,3.16；Br,22.74；ESI-MS (m/z) (M+): theoretical value 349.99, measured value are 350.55。
(2) under nitrogen protection, weigh 0.01mol intermediate S-2 to be dissolved in tetrahydrofuran, be cooled to -78 DEG C, then to The tetrahydrofuran solution of 8ml 1.6mol/L n-BuLi is added in reaction system, is added after reacting 3h at -78 DEG C 0.013mol triisopropyl borate ester reacts 2h, and reaction system is then risen to 0 DEG C, and 10ml 2mol/L hydrochloric acid solution is added, stirs 3h is mixed, ether extraction is added in fully reacting, and anhydrous magnesium sulfate drying is added in extract liquor, and revolving is recrystallized with alcohol solvent, obtained To intermediate M-2；Elemental analysis structure (molecular formula C19H13BO4): theoretical value C, 72.19；H,4.15；B,3.42；Test value: C, 72.19；H,4.15；B,3.43.ESI-MS(m/z)(M+): theoretical value 316.09, measured value 316.49.
Intermediate M is prepared with the synthetic method of intermediate M-1, specific structure is as shown in table 1.
Table 1
Embodiment 2: the synthesis of compound 3:
In 250mL there-necked flask, 0.01mol raw material A -1 and 0.012mol intermediate M-1 are dissolved in toluene and ethyl alcohol 150mL(VToluene: VEthyl alcohol=5:1) in mixed solution, 0.0002mol Pd (PPh is added after deoxygenation3)4With 0.02mol K2CO3, Inert atmosphere lower 110 DEG C of 24 hours of reaction, after raw material fully reacting, filtrate is rotated and removes solvent, slightly by cooling, filtering Product crosses silicagel column, obtains target product；Elemental analysis structure (molecular formula C47H32O2): theoretical value C, 89.78；H,5.13；It surveys Examination value: C, 89.77；H,5.13；ESI-MS (m/z) (M+): theoretical value 628.24, measured value 628.55.
Embodiment 3: the synthesis of compound 10:
In 250mL there-necked flask, 0.01mol raw material A -2 and 0.012mol intermediate M-2 are dissolved in toluene and ethyl alcohol 150mL(VToluene: VEthyl alcohol=5:1) in mixed solution, 0.0002mol Pd (PPh is added after deoxygenation3)4With 0.02mol K2CO3, Inert atmosphere lower 110 DEG C of 24 hours of reaction, after raw material fully reacting, filtrate is rotated and removes solvent, slightly by cooling, filtering Product crosses silicagel column, obtains target product；Elemental analysis structure (molecular formula C44H26O3): theoretical value C, 87.69；H,4.35；It surveys Examination value: C, 87.68；H,4.35；ESI-MS (m/z) (M+): theoretical value 602.19, measured value 602.77.
Embodiment 4: the synthesis of compound 19:
The preparation method of compound 19, the difference is that replacing raw material A -1 with raw material A -2, uses intermediate with embodiment 2 M-3 replaces intermediate M-1.Elemental analysis structure (molecular formula C44H26O3): theoretical value C, 87.69；H,4.35；Test value: C, 87.70；H,4.35.ESI-MS(m/z)(M+): theoretical value 602.19, measured value 602.61.
Embodiment 5: the synthesis of compound 20:
The preparation method of compound 20, the difference is that replacing raw material A -1 with raw material A -3, uses intermediate with embodiment 2 M-3 replaces intermediate M-1.Elemental analysis structure (molecular formula C44H26O3): theoretical value C, 87.69；H,4.35；Test value: C, 87.69；H,4.35.ESI-MS(m/z)(M+): theoretical value 602.19, measured value 602.74.
Embodiment 6: the synthesis of compound 28:
In 250mL there-necked flask, under nitrogen atmosphere, weighs 0.01mol raw material A -2 and be dissolved in 100ml tetrahydrofuran, then 0.012mol raw material B-1 and 0.0002mol tetrakis triphenylphosphine palladium is added, mixture is stirred, adds 0.02mol potassium carbonate The mixed solution of above-mentioned reactant is heated to reflux 20 hours by aqueous solution at 90 DEG C of reaction temperature；After reaction, cooling to add Water, mixture are extracted with dichloromethane, and extract liquor is dried, filtered and is concentrated under reduced pressure with anhydrous sodium sulfate, gained residue Silica gel column purification is crossed, target compound is obtained；Elemental analysis structure (molecular formula C38H22O3): theoretical value C, 86.67；H,4.21； Test value: C, 86.66；H,4.21.ESI-MS(m/z)(M+): theoretical value 526.16, measured value 526.74.
Embodiment 7: the synthesis of compound 39:
The preparation method of compound 39 with embodiment 2, the difference is that, with intermediate M-4 replace intermediate M-1.Member Element analysis structure (molecular formula C47H32O2): theoretical value C, 89.78；H,5.13；Test value: C, 89.79；H,5.13.ESI-MS(m/ z)(M+): theoretical value 628.24, measured value 628.53.
Embodiment 8: the synthesis of compound 50:
The preparation method of compound 50, the difference is that replacing raw material A -1 with raw material A -4, uses intermediate with embodiment 2 M-5 replaces intermediate M-1.Elemental analysis structure (molecular formula C44H26O3): theoretical value C, 87.69；H,4.35；Test value: C, 87.68；H,4.35.ESI-MS(m/z)(M+): theoretical value 602.19, measured value 602.49.
Embodiment 9: the synthesis of compound 61:
The preparation method of compound 61, the difference is that replacing raw material A -1 with raw material A -5, uses intermediate with embodiment 2 M-6 replaces intermediate M-1.Elemental analysis structure (molecular formula C44H26O3): theoretical value C, 87.69；H,4.35；Test value: C, 87.69；H,4.34.ESI-MS(m/z)(M+): theoretical value 602.19, measured value 602.82.
Embodiment 10: the synthesis of compound 69:
In 250mL there-necked flask, under nitrogen atmosphere, weighs 0.01mol raw material A -6 and be dissolved in 100ml tetrahydrofuran, then 0.012mol raw material B-2 and 0.0002mol tetrakis triphenylphosphine palladium is added, mixture is stirred, adds 0.02mol potassium carbonate The mixed solution of above-mentioned reactant is heated to reflux 20 hours by aqueous solution at 90 DEG C of reaction temperature；After reaction, cooling to add Water, mixture are extracted with dichloromethane, and extract liquor is dried, filtered and is concentrated under reduced pressure with anhydrous sodium sulfate, gained residue Silica gel column purification is crossed, target compound is obtained；Elemental analysis structure (molecular formula C41H28O2): theoretical value C, 89.10；H,5.11； Test value: C, 89.10；H,5.12.ESI-MS(m/z)(M+): theoretical value 552.21, measured value 552.54.
Embodiment 11: the synthesis of compound 73:
The preparation method of compound 73, the difference is that replacing raw material A -1 with raw material A -2, uses intermediate with embodiment 2 M-7 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.47；H,4.47.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.74.
Embodiment 12: the synthesis of compound 83:
The preparation method of compound 83, the difference is that replacing raw material A -1 with raw material A -3, uses intermediate with embodiment 2 M-8 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.46；H,4.46.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.81.
Embodiment 13: the synthesis of compound 96:
The preparation method of compound 96, the difference is that replacing raw material A -1 with raw material A -6, uses intermediate with embodiment 2 M-9 replaces intermediate M-1.Elemental analysis structure (molecular formula C53H36O2): theoretical value C, 90.31；H,5.15；Test value: C, 90.31；H,5.14.ESI-MS(m/z)(M+): theoretical value 704.27, measured value 704.91.
Embodiment 14: the synthesis of compound 115:
The preparation method of compound 115 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -5, with centre Body M-10 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.47；H,4.47.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.88.
Embodiment 15: the synthesis of compound 128:
The preparation method of compound 128 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -3, with centre Body M-11 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.46；H,4.46.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.76.
Embodiment 16: the synthesis of compound 144:
The preparation method of compound 144 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -4, with centre Body M-12 replaces intermediate M-1.Elemental analysis structure (molecular formula C53H36O2): theoretical value C, 90.31；H,5.15；Test value: C, 90.30；H,5.15.ESI-MS(m/z)(M+): theoretical value 704.27, measured value 704.74.
Embodiment 17: the synthesis of compound 155:
The preparation method of compound 155 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -3, with centre Body M-13 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.46；H,4.46.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.84.
Embodiment 18: the synthesis of compound 163:
163 preparation method of compound, the difference is that replacing raw material A -1 with raw material A -2, uses intermediate with embodiment 2 M-14 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.46；H,4.46.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.46.
Embodiment 19: the synthesis of compound 177:
177 preparation method of compound, the difference is that replacing raw material A -1 with raw material A -6, uses intermediate with embodiment 2 M-15 replaces intermediate M-1.Elemental analysis structure (molecular formula C53H36O2): theoretical value C, 90.31；H,5.15；Test value: C, 90.31；H,5.15.ESI-MS(m/z)(M+): theoretical value 704.27, measured value 704.89.
Embodiment 20: the synthesis of compound 196:
The preparation method of compound 196 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -5, with centre Body M-16 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.47；H,4.45.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.86.
Embodiment 21: the synthesis of compound 218:
The preparation method of compound 218 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -3, with centre Body M-17 replaces intermediate M-1.Elemental analysis structure (molecular formula C50H30O3): theoretical value C, 88.47；H,4.46；Test value: C, 88.46；H,4.46.ESI-MS(m/z)(M+): theoretical value 678.22, measured value 678.59.
Embodiment 22: the synthesis of compound 231:
The preparation method of compound 231 is with embodiment 2, the difference is that raw material A -1 is replaced with raw material A -6, with centre Body M-18 replaces intermediate M-1.Elemental analysis structure (molecular formula C53H36O2): theoretical value C, 90.31；H,5.15；Test value: C, 90.30；H,5.15.ESI-MS(m/z)(M+): theoretical value 704.27, measured value 704.95.
Embodiment 23: the synthesis of compound 242:
The preparation method of compound 242, the difference is that replacing raw material B-1 with raw material C-1, uses raw material with embodiment 6 A-4 replaces raw material A -1.Elemental analysis structure (molecular formula C41H28O2): theoretical value C, 89.10；H,5.11；Test value: C, 89.11；H,5.11.ESI-MS(m/z)(M+): theoretical value 552.21, measured value 552.74.
Embodiment 24: the synthesis of compound 261:
The preparation method of compound 261, the difference is that replacing raw material B-1 with raw material D-1, uses raw material with embodiment 6 A-6 replaces raw material A -1.Elemental analysis structure (molecular formula C54H38O): theoretical value C, 92.27；H,5.45；Test value: C, 92.26；H,5.45.ESI-MS(m/z)(M+): theoretical value 702.29, measured value 702.66.
This organic compound uses in luminescent device, has high Tg (glass transition temperature) temperature and triplet (T1), suitable HOMO, lumo energy can be used as hole barrier/electron transport material and use, and also can be used as emitting layer material makes With.Hot property, T1 energy level and the test of HOMO energy level are carried out respectively to the compounds of this invention and current material, as a result such as 2 institute of table Show.
Table 2
Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2*10-5's Toluene solution；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimeter) Measurement, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in Japanese Shimadzu Corporation TGA-50H thermogravimetric analyzer on be measured, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy level be by Ionizing energy test macro (IPS3) test, is tested as atmospheric environment.
By upper table data it is found that CBP the and TPBi material that comparison is applied at present, organic compound of the invention have high Glass transition temperature can be improved material membrane phase stability, further increase device service life；With high triplet state energy Grade, can stop luminescent layer energy loss, to promote device light emitting efficiency.Material of the present invention and application material have phase simultaneously As HOMO energy level.Therefore, the present invention contains the organic material of ketone after the different function layer for being applied to OLED device, can be effective Improve the luminous efficiency and service life of device.
Below by way of device embodiments 1~23 and device comparative example 1 OLED material that the present invention will be described in detail synthesizes in device Application effect in part.Device embodiments 2~23 of the present invention, the device compared with device embodiments 1 of device comparative example 1 Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material is also kept Unanimously, except that the emitting layer material in 2~15 pairs of devices of device embodiments converts；16~23 pairs of device embodiments Hole barrier/electron transport layer materials of device convert, the performance test results of each embodiment obtained device such as 3 institute of table Show.
Device embodiments 1:
As shown in Figure 1, a kind of electroluminescent device, preparation step includes: ITO sun a) cleaned on transparent substrate layer 1 Pole layer 2 is cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate respectively, 2 points is then handled in plasma cleaner Clock；B) on ito anode layer 2, hole injection layer material HAT-CN is deposited by vacuum evaporation mode, with a thickness of 10nm, this layer As hole injection layer 3；C) on hole injection layer 3, hole mobile material NPB is deposited by vacuum evaporation mode, with a thickness of 80nm, the layer are hole transmission layer/electronic barrier layer 4；D) luminescent layer 5 is deposited on hole transport/electronic barrier layer 4, it is main Body material is the compound 10 and compound GH of preparation of the embodiment of the present invention, and dopant material is Ir (ppy)3, compound 10, GH and Ir(ppy)3Three's mass ratio is 50:50:10, with a thickness of 30nm；E) it on luminescent layer 5, is steamed by vacuum evaporation mode Electron transport material TPBI is plated, with a thickness of 40nm, this layer of organic material is used as hole barrier/electron transfer layer 6；F) in sky On cave blocking/electron transfer layer 6, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electron injecting layer 7；G) exist On electron injecting layer 7, vacuum evaporation cathode Al (100nm), the layer is cathode reflection electrode layer 8；It is completed according to above-mentioned steps After the production of electroluminescent device, the driving voltage of measurement device, current efficiency, the result is shown in shown in table 3.Point of associated materials Subformula is as follows:
Device embodiments 2:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 19, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 3:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 28, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 4:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 50, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 5:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 61, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 6:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 69, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 7:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 73, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 8:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 96, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 9:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 115, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 10:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 144, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 11:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 163, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 12:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 177, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 13:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 196, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 14:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 231, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 15:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: preparation of the embodiment of the present invention Compound 261, GH and Ir (ppy)3Constituted by weight 50:50:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 16:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 3)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 17:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 20)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 18:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 39)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 19:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 83)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 20:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 128)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 21:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 155)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 22:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 218)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 23:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: the chemical combination of preparation of the embodiment of the present invention Object 242)/electron injecting layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device comparative example 1:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 80nm, material: NPB)/luminescent layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3By weight Amount is constituted than 90:10 blending)/hole barrier/electron transfer layer 6 (thickness: 35nm, material: TPBI)/electron injecting layer 7 (thickness Degree: 1nm, material: LiF)/Al (thickness: 100nm).The detection data of gained electroluminescent device is shown in Table 3.
Table 3
Organic compound of the present invention can be applied to the production of OLED luminescent device it can be seen from the result of table 3, and with than It is compared compared with example, either efficiency or service life obtain larger change, the especially service life of device than known OLED material Obtain biggish promotion.
Work limitation rate is also more stable at low temperature for the OLED device of further material preparation of the present invention, by device reality It applies example 4,12,21 and device comparative example 1 and carries out efficiency test in -10~80 DEG C of sections, acquired results are as shown in table 4 and Fig. 2.
Table 4
From the data of table 4 and Fig. 2 it is found that device embodiments 4,12,21 are material of the present invention and the device that known materials are arranged in pairs or groups Part structure is compared with device comparative example 1, 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 (10)

1. a kind of compound containing ketone, which is characterized in that shown in the structure of the compound such as general formula (1):
In general formula (1), Ar2It is expressed as the C for being substituted or being unsubstituted1-10Alkyl, the C for replacing or being unsubstituted6-30Aryl, warp The C for replacing or being unsubstituted5-30One of heteroaryl；
In general formula (1), Ar1、Ar3The C for being expressed as singly-bound, being substituted or being unsubstituted independently6-30Arlydene is substituted Or the C being unsubstituted5-30One of inferior heteroaryl；Ar1It is also denoted as the C for being substituted or being unsubstituted1-10Alkyl, warp The C for replacing or being unsubstituted6-30Aryl, the C for being substituted or being unsubstituted5-30One of heteroaryl；
In general formula (1), X is expressed as carbon atom, oxygen atom or sulphur atom；
When X is carbon atom, k=1, m, n independently be expressed as 0 or 1, and m, n be not identical；
When X is oxygen atom or sulphur atom, k=0, m=0, n=1；
In general formula (1), X1、X2Independently be expressed as singly-bound, oxygen atom, C1-10The alkylidene of linear or branched alkyl group substitution, One of the imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl that aryl replaces replace；X1、X2At least one is single Key.
2. compound according to claim 1, which is characterized in that the structure of the compound such as general formula (2), general formula (3), Shown in general formula (4) or general formula (5):
3. compound according to claim 1, which is characterized in that the Ar1、Ar3Separately it is expressed as singly-bound, Asia One of phenyl, biphenylene or naphthylene；Ar1It is also denoted as one of methyl, phenyl, xenyl or naphthalene；
Ar2It is expressed as one of methyl, phenyl, xenyl or naphthalene.
4. compound according to claim 1, which is characterized in that in the general formula (1)It indicates are as follows:One of.
5. compound according to claim 1, which is characterized in that the concrete structure formula of the compound are as follows:
Any one of.
6. a kind of preparation method of compound as claimed in any one of claims 1 to 5, which is characterized in that sent out in preparation process Raw reaction equation are as follows:
(1) when X is oxygen atom or sulphur atom, k=0, m=0, n=1:
Work as Ar3When not indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
Raw material A and intermediate M are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4And K2CO3, 95~110 DEG C of 10~24 hours of reaction under inert atmosphere；After raw material fully reacting, filtrate is rotated and is removed by cooling, filtering Solvent, crude product cross silicagel column, obtain target compound；
Wherein, the dosage of the toluene and ethyl alcohol is that every gram of raw material A uses 30~50mL toluene and 5~10mL ethyl alcohol, intermediate The molar ratio of body M and raw material A is (1~1.5): 1, Pd (PPh3)4Molar ratio with raw material A is (0.006~0.02): 1, K2CO3 Molar ratio with raw material A is (1.5~2): 1；
Work as Ar3When indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
It under nitrogen atmosphere, weighs raw material A and is dissolved in tetrahydrofuran, then raw material B and tetrakis triphenylphosphine palladium are added, stirring is mixed Object is closed, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux 5-20 at 70-90 DEG C of reaction temperature Hour；After reaction, cooling plus water, mixture are extracted with dichloromethane, extract liquor dried, filtered with anhydrous sodium sulfate and The lower concentration of decompression, gained residue cross silica gel column purification, obtain target compound；
Wherein, the raw material A and the molar ratio of raw material B are 1:(1.0~1.5), the molar ratio of tetrakis triphenylphosphine palladium and raw material A For (0.001~0.02): 1, the molar ratio of potassium carbonate and raw material A is (1.0~2.0): 1, THF and the amount ratio of raw material A be 1g: (10~30) ml.
(2) when X is carbon atom, k=1, m=0, n=1:
Work as Ar3When not indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
Raw material A and intermediate N are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4And K2CO3, 95~110 DEG C of 10~24 hours of reaction under inert atmosphere；After raw material fully reacting, filtrate is rotated and is removed by cooling, filtering Solvent, crude product cross silicagel column, obtain target compound；
Wherein, the dosage of the toluene and ethyl alcohol is that every gram of raw material A uses 30~50mL toluene and 5~10mL ethyl alcohol, intermediate The molar ratio of body N and raw material A is (1~1.5): 1, Pd (PPh3)4Molar ratio with raw material A is (0.006~0.02): 1, K2CO3 Molar ratio with raw material A is (1.5~2): 1；
Work as Ar3When indicating singly-bound:
The specific reaction process of above-mentioned reaction equation are as follows:
It under nitrogen atmosphere, weighs raw material A and is dissolved in tetrahydrofuran, then raw material C and tetrakis triphenylphosphine palladium are added, stirring is mixed Object is closed, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux 5-20 at 70-90 DEG C of reaction temperature Hour；After reaction, cooling plus water, mixture are extracted with dichloromethane, extract liquor dried, filtered with anhydrous sodium sulfate and The lower concentration of decompression, gained residue cross silica gel column purification, obtain target compound；
Wherein, the raw material A and the molar ratio of raw material C are 1:(1.0~1.5), the molar ratio of tetrakis triphenylphosphine palladium and raw material A For (0.001~0.02): 1, the molar ratio of potassium carbonate and raw material A is (1.0~2.0): 1, THF and the amount ratio of raw material A be 1g: (10~30) ml；
(3) when X is carbon atom, k=1, m=1, n=0:
Specific reaction process are as follows:
It under nitrogen atmosphere, weighs raw material A and is dissolved in tetrahydrofuran, then raw material D and tetrakis triphenylphosphine palladium are added, stirring is mixed Object is closed, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux 5-20 at 70-90 DEG C of reaction temperature Hour；After reaction, cooling plus water, mixture are extracted with dichloromethane, extract liquor dried, filtered with anhydrous sodium sulfate and The lower concentration of decompression, gained residue cross silica gel column purification, obtain target compound；
The molar ratio of the raw material A and raw material D are 1:1.0~1.5, and the molar ratio of tetrakis triphenylphosphine palladium and raw material A is 0.001 The molar ratio of~0.02:1, potassium carbonate and raw material A is 1.0~2.0:1, and the amount ratio of raw material A and THF are 1g:10~30ml.
7. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer Contain the described in any item compounds containing ketone of Claims 1 to 5.
8. organic electroluminescence device according to claim 7, which is characterized in that including luminescent layer, the luminescent layer contains It has the right to require 1~5 described in any item compounds containing ketone.
9. organic electroluminescence device according to claim 7, which is characterized in that including hole blocking layer/electron-transport Layer, the hole blocking layer/electron transfer layer contain the described in any item compounds containing ketone of Claims 1 to 5.
10. a kind of illumination or display element, which is characterized in that including the described in any item organic electroluminescence hairs of such as claim 7-9 Optical device.
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JP2011231033A (en) * 2010-04-26 2011-11-17 Canon Inc Novel 10,10-dialkylanthrone compound and organic light-emitting device including the same
CN102870248A (en) * 2010-04-26 2013-01-09 佳能株式会社 Organic light-emitting device
CN103189368A (en) * 2010-11-08 2013-07-03 佳能株式会社 Thioxanthone compound and organic light emitting element having the same
CN106467542A (en) * 2016-08-18 2017-03-01 江苏三月光电科技有限公司 A kind of compound with anthrone as core and its application
CN106831744A (en) * 2016-12-30 2017-06-13 上海天马有机发光显示技术有限公司 A kind of electroluminescent organic material and organic photoelectric device

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JP2011231033A (en) * 2010-04-26 2011-11-17 Canon Inc Novel 10,10-dialkylanthrone compound and organic light-emitting device including the same
CN102870248A (en) * 2010-04-26 2013-01-09 佳能株式会社 Organic light-emitting device
CN103189368A (en) * 2010-11-08 2013-07-03 佳能株式会社 Thioxanthone compound and organic light emitting element having the same
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CN106831744A (en) * 2016-12-30 2017-06-13 上海天马有机发光显示技术有限公司 A kind of electroluminescent organic material and organic photoelectric device

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