CN106083824A - Organic photoelectrical material and include the organic electroluminescence device of this organic material - Google Patents

Organic photoelectrical material and include the organic electroluminescence device of this organic material Download PDF

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CN106083824A
CN106083824A CN201610403374.7A CN201610403374A CN106083824A CN 106083824 A CN106083824 A CN 106083824A CN 201610403374 A CN201610403374 A CN 201610403374A CN 106083824 A CN106083824 A CN 106083824A
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organic
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electroluminescence device
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CN106083824B (en
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盛磊
张鑫鑫
石宇
胡葆华
孟凡民
周银波
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Valiant Co Ltd
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Valiant Co Ltd
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Priority to CN201610403374.7A priority Critical patent/CN106083824B/en
Priority to CN201910086074.4A priority patent/CN109796964A/en
Priority to CN201910086099.4A priority patent/CN109796435B/en
Priority to PCT/CN2016/090641 priority patent/WO2017210966A1/en
Priority to KR1020197000163A priority patent/KR102138087B1/en
Priority to TW105129721A priority patent/TWI624465B/en
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Abstract

The present invention relates to a kind of organic photoelectrical material and include the organic electroluminescence device of this organic material, organic photoelectrical material by shown in following formula I, wherein R1And R2It is each independently selected from the one in hydrogen-based, cyano group, isothiocyano and phenyl, R3、R4、R5、R6、R7And R8Being each independently selected from hydrogen-based, halogen and carbon number is 10～50 and containing the one in the aromatic heterocyclic radical of at least one in N, S, O.This organic photoelectrical material, can apply in organic electroluminescence device as luminescent material, thus improve the maximum current efficiency of organic electroluminescence device, reduce the bright voltage that opens of organic electroluminescence device, and make the spectral coverage of the visible ray sent of organic electroluminescence device wider.

Description

Organic photoelectrical material and include the organic electroluminescence device of this organic material
Technical field
The present invention relates to field of photoelectric technology, particularly relate to a kind of organic photoelectrical material and include this organic photoelectrical material Organic electroluminescence device.
Background technology
Organic electroluminescence device (being called for short OLED) results from the eighties in last century, and compared with liquid crystal display, OLED has Self-luminous, wide viewing angle, fast response time, the plurality of advantages such as Flexible Displays can be realized, thus receive significant attention.
Organic electroluminescence device is the luminescent device that a kind of electric current drives, and according to the difference of luminous mechanism, can be divided into Fluorescent device and phosphorescent devices two kinds, when electric charge is from electrode injection device, due to the randomness in electron spin direction, singlet state The ratio of exciton only has 25%, and other 75% is triplet exciton, and generally, fluorescent device is only with singlet excited Excitonic luminescence, and phosphorescent devices can apply the energy of singlet excitons and triplet exciton simultaneously, therefore, the effect of phosphorescent devices Rate is much larger than fluorescent device.
The efficiency of phosphorescent devices is higher than fluorescent device, and but, phosphorescent devices also has its weak point, as phosphor material is main It is the coordination compound of the coordination compound containing noble metal, particularly metal iridium and platinum, owing to metal iridium and platinum itself are expensive, because of This, the price of phosphor material is extremely expensive, which also limits the application space of phosphor material.
Therefore, application fluorescent material is as light emitting molecule, and is capable of the OLED of High Efficiency Luminescence, such Research direction seems very attractive.
2012, C.Adachi published thesis (Nature., 2012,492,234) on Nature, it was recently reported that Yi Zhongji In thermal activation delayed fluorescence (TADF) mechanism, it is achieved the fluorescent device of High Efficiency Luminescence, this is the making of high efficiency fluorescent device, band Carry out new direction.In existing scope of human knowledge, TADF material, need that there is electron donor (being called for short D) and electron acceptor (is called for short A), the D-A type structure thus formed, it is possible to realize the molecular structure requirement of delayed fluorescence.
Summary of the invention
In order to solve the problems referred to above, the invention provides a kind of organic photoelectrical material, it is possible to apply as luminescent material In organic electroluminescence device, thus improve the maximum current efficiency of organic electroluminescence device, reduce organic electroluminescence and send out Optical device open bright voltage, and make the spectral coverage of the visible ray sent of organic electroluminescence device wider.
It is an object of the invention to provide a kind of organic photoelectrical material, shown in following formula I.
In above-mentioned formula I, R1And R2It is each independently selected from hydrogen-based, cyano group (-CN), isothiocyano (-NCS) and phenylIn one, R3、R4、R5、R6、R7And R8Being each independently selected from hydrogen-based, halogen and carbon number is 10～50 And containing the one in the aromatic heterocyclic radical of at least one in N, S, O.Wherein, halogen can select according to the actual requirements, The most fluorine-based, chloro, bromo, further, it is preferable to be fluorine-based.In substituent group, preferably R1And R2Identical, R3、R4、R5、R6、 R7And R8Can be mutually the same, it is also possible to mutually differ, it is also possible to be that therein arbitrarily both or both above the most identical, It is not exposed to concrete restriction.
In above-mentioned formula I, as the example of aromatic heterocyclic radical, annelated heterocycles base, monocyclic aromatic heterocycle base and many can be enumerated Aromatic heterocycle radical etc., wherein annelated heterocycles base, can be obtained by monocyclic aromatic or non-aromatic heterocyclic (heterocycle can be different) condensation Arrive, additionally, described aromatic heterocyclic radical can also be in above-mentioned annelated heterocycles base, monocyclic aromatic heterocycle base or polycyclic aromatic heterocyclic radical Obtained by after at least one group bonding in aryl, halogenated aryl and aryl amine, wherein, aryl can enumerate phenyl, aralkyl Base, at least containing the aryl such as xenyl of a phenyl, halogenated aryl is institute after aryl is replaced by least one in F, Cl, Br The group formed, wherein aryl is replaced by preferably F, and aryl amine can enumerate hexichol amido, certainly it is noted that enumerate several Typical group, is not exposed to concrete restriction.When containing N, S, O hetero atom, heteroatomic number is not exposed to concrete Limit, such as, can be 1,2,3,4,5,6 or 7, it addition, in a substituent group, can choose above-mentioned Any one in hetero atom, it is also possible to for any two kinds or three kinds in above-mentioned hetero atom.Preferably, carbon number is selected It is the aromatic heterocyclic radical of 11～40, it is further preferred that the aromatic heterocyclic radical selecting carbon number to be 11～36.
Preferably, one or more in the group shown in following formula (1)～formula (21) of described aromatic heterocyclic radical:
In above-mentioned formula (1), formula (4), formula (9), formula (12) and formula (17), R9And R10It is each independently selected from hydrogen-based, carbon Aryl that alkyl that atomic number is 1～10, carbon number are 6～10, carbon number be 6～20 aryl amine and containing N and Carbon number is the one in the annelated heterocycles base of 12～20, R11Selected from hydrogen-based or alkyl that carbon number is 1～10；Above-mentioned In formula (1)～formula (16), L represents the group of bonding, and L is 6～20 selected from the arlydene that carbon number is 6～20, carbon number Halo arlydene and sub-virtue cyano group in one, wherein, halogen atom is F, Cl, Br, preferably F；Above-mentioned formula (17)～formula (21) in, M represents the group of bonding, and M is in the secondary aryl that carbon number is 6～20, halo time aryl and secondary virtue cyano group One, wherein, halogen atom is F, Cl, Br, preferably F.
At R9、R10And R11In, substituent group is as described below.
Carbon number is the alkyl of 1～10, chain-like alkyl and cycloalkyl, and wherein chain-like alkyl includes again straight chained alkyl And branched alkyl, additionally, the hydrogen on chain-like alkyl also can be replaced by cycloalkyl, same, the hydrogen being positioned in cycloalkyl also may be used Replaced by alkyl.Preferably, the alkyl selecting carbon number to be 1～6, it is further preferred that selecting carbon number is 1～4 Alkyl group, carbon number is the cycloalkyl of 5～6.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, different Propyl group, normal-butyl, the tert-butyl group.
Carbon number is the aryl of 6～10, such as, can enumerate phenyl, aralkyl etc..Preferably, selecting carbon number is 6 ～the aryl of 9, it is further preferred that the aryl selecting carbon number to be 6～8.
Carbon number is the aryl amine of 6～20, can be by such as ammonia (NH3Hydrogen on) is formed after being replaced by aryl such as phenyl Group, concretely hexichol amido, wherein the replacement number of aryl can be 1,2 or 3, and wherein mentioned aryl is excellent Choose and state the aryl being previously mentioned, so repeating the most one by one.Preferably, the aryl amine selecting carbon number to be 12～20, enters one Preferably, selection carbon number is the aryl amine of 12～16 to step.
Containing N and the example of annelated heterocycles base that carbon number is 12～20, carbazyl can be enumerated.Preferably, select Containing N and annelated heterocycles base that carbon number is 12～16.
In above-mentioned formula (1)～formula (16), L group is as described below.
Carbon number is the arlydene of 6～20, such as, can be that phenylene, sub-benzene alkyl are as containing methyl or the tert-butyl group Phenyl, at least contain the arylene group such as biphenylene of a phenyl, sub-condensed-nuclei aromatics base, wherein at biphenylene and sub-condensed ring Carbon on aryl can be bonded alkyl and/or thiazolinyl, wherein alkyl such as methyl, the tert-butyl group.Preferably, selection carbon number is The arlydene of 6～14, it is further preferred that the arlydene selecting carbon number to be 6～12, it is further preferred that select carbon Atomic number is the arlydene of 6～8.As the example of arlydene, specifically can enumerate:
Carbon number is the halo arlydene of 6～20, the group formed after being replaced by halogen atom for arlydene, the most preferably Arlydene mentioned above is replaced by halogen atom such as fluorine, and preferably carbon number is the fluoro arlydene of 6～20.Preferably, The halo arlydene selecting carbon number to be 6～14, it is further preferred that the halo arlydene selecting carbon number to be 6～14, It is further preferred that the halo arlydene selecting carbon number to be 6～12.As the example of halo arlydene, the most permissible Enumerate:
Sub-virtue cyano group is the group formed after arlydene is replaced by cyano group, and arlydene the most mentioned above is by cyano group Replaced.
In above-mentioned formula (17)～formula (21), M group is as described below.
Carbon number is the secondary aryl of 6～20, can carry out with other groups being bonded for having three on aromatic compound Group.Preferably, secondary aryl selecting carbon number to be 6～14, it is further preferred that select carbon number be 6～12 secondary Aryl.As the example of secondary aryl, specifically can enumerate:
The above-mentioned halo mentioned time aryl and secondary virtue cyano group are replaced institute's shape by halogen atom or cyano group successively for time aryl The group become, is preferably replaced by F.
Organic photoelectrical material provided by the present invention, is the small molecule material containing acenaphtho pyrazine structure, by containing Selecting other chemical groups to modify in the structure of acenaphtho pyrazine, concrete selected chemical group is as it has been described above, at this not Repeat the most one by one, so that this organic photoelectrical material has D-A type or D-A-D type molecular structure unit, the namely present invention The organic photoelectrical material provided both had contained electron acceptor core, contained again electron donor, then this organic photoelectrical material has excellent Fluorescent emission ability, there is suitable molecular entergy level, moderate molecular mass, good thin film stability, be suitable as little The functional layer of molecule organic electroluminescent device, applies in field of organic electroluminescence, and especially, this organic photoelectrical material can It is preferably applied in the luminescent layer in little molecule organic electroluminescent device as luminescent material.
After the organic photoelectrical material that the present invention provides is applied in organic electroluminescence device as luminescent material so that have Organic electroluminescence devices can send the visible ray of different colours, and the skyst blue, cyan, green, the color such as orange, spectrum covers Scope is relatively wide, and improves the performance of organic electroluminescence device, as the maximum current efficiency of device being greatly improved, simultaneously Reduce and open bright voltage.
As the example of organic photoelectrical material, specifically can enumerate following compound C001～C372, wherein need explanation , following compound is to meet present invention spirit and the representative structure of principle, it will be appreciated that list the concrete of following compound Structure, is intended merely to preferably explain the present invention, is not limitation of the present invention.
The concrete preparation method of the electroluminescent organic material provided in the present invention, will retouch in embodiment later in detail State, synthetic route associated therewith and preparation technology, the conventional steps being in organic synthesis field and conventional selection, at this not Repeat again.
Another object of the present invention is to provide a kind of organic electroluminescence device, including negative electrode, anode and luminescent layer, institute Stating luminescent layer between anode and negative electrode, wherein said luminescent layer is by including prepared by organic photoelectrical material provided by the present invention Obtain.
Additionally, in above-mentioned organic electroluminescence device, may also include hole transmission layer, electron transfer layer and electronics and inject Layer, wherein, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer are respectively positioned between negative electrode and anode, on anode Hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer are sequentially stacked it.
In above-mentioned organic electroluminescence device, anode is preferably tin indium oxide (being called for short ITO) electro-conductive glass, hole transport Layer preferably NPB prepares, and the preferred material provided by the present invention of luminescent layer and mCP prepare jointly, electron transfer layer by TPBI prepares, and electron injecting layer is prepared by LiF, and the preferred Al of negative electrode, wherein NPB, mCP and TPBI are as follows.
In above-mentioned organic electroluminescence device, each functional layer is not limited to use above-mentioned mentioned material, these Material can replace with other material, and as hole transmission layer can be prepared by TAPC, electron transfer layer can be by TpPYPB Preparing, wherein TAPC and TpPYPB is as follows:
In above-mentioned organic electroluminescence device, each film layer above-mentioned, say, that hole transmission layer, luminescent layer, electronics Transport layer all can pass through the methods such as vapour deposition method, spin-coating method or casting method by material system corresponding for each film layer with electron injecting layer Thin film is become to be formed.Additionally, for the material film of each film layer and be easily obtained uniform film layer, meanwhile, be difficult to Generate pin hole, preferably vacuum vapour deposition.When selecting vacuum vapour deposition, wherein heating-up temperature, vacuum, evaporation rate and substrate Temperature can carry out routine according to the actual requirements and select.It is prone to obtain when selecting vacuum vapour deposition by corresponding material film Obtain uniform film layer, and be difficult to generate pin hole.
The organic electroluminescence that the present invention provides selects conventional method to prepare, and there is no special demand.
In the organic electroluminescence device that the present invention provides, due to the organic photoelectrical material provided containing the present invention, it is possible to It is greatly improved the maximum current efficiency of organic electroluminescence device, meanwhile, also reduces and open bright voltage, significantly improved The service life of organic electroluminescence devices.
Accompanying drawing explanation
The structural representation of the organic electroluminescence device that Fig. 1 is provided by the embodiment of the present invention.
Drawing reference numeral illustrates:
101-anode, 102-hole transmission layer, 103-luminescent layer, 104-electron transfer layer, 105-electron injecting layer, 106- Negative electrode.
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention will become more along with these explanations For clear, clear and definite.
Embodiment
The present invention is further described below by way of instantiation.But these examples are the most exemplary, not to this The protection domain of invention constitutes any restriction.
In the following embodiments, the reagent, material and the instrument that are used such as do not have special explanation, are conventional examination Agent, conventional material and conventional instrument, the most commercially available, wherein involved reagent also can be synthesized by conventional synthesis process Obtain.
The preparation of embodiment one compound
The preparation of embodiment 1 compound 1
5-bromine acenaphthenequinone (26.1g, 0.1mol), ethylenediamine (13g, 0.12mol) and glacial acetic acid is added in 1L there-necked flask (300mL), it is warming up to backflow, in air atmosphere, after insulation reaction 12h, is down to room temperature, afterwards, reactant liquor is poured into In the deionized water of 1000mL, after stirring reaction 0.5h, sucking filtration, and select 500mL deionized water drip washing filter cake, then select 150mL dehydrated alcohol drip washing filter cake, collects filter cake, it is thus achieved that compound 1 is 22.2g, and being computed yield is 78%, Mass Spectrometer Method (being called for short MS) (m/z): 281.9.
Embodiment 2-embodiment 11 compound 2～the preparation of compound 11
Compound 2～11 is prepared the most by the following method:
The method be given according to embodiment 1 and proportioning raw materials, wherein using different types of substrate is raw material, equal and second Diamidogen carries out ring closure reaction, the most in various embodiments, selected raw material and obtain corresponding compound and yield and Mass Spectrometer Method result is as shown in table 1 below.
Table 1
The preparation of embodiment 12 compound 12
In 1L there-necked flask, add 5-bromine acenaphthenequinone (26.1g, 0.1mol), two amido Maleic nitrile (13g, 0.12mol) and ice Acetic acid (300mL), is warming up to backflow, after insulation reaction 6h, is down to room temperature, reactant liquor is poured into 1000mL deionized water afterwards In, stir 0.5h, then sucking filtration, then select 500mL deionized water drip washing filter cake, then select 150mL dehydrated alcohol drip washing filter After cake, collecting filter cake, obtaining compound 12 is 28.6g, and being computed yield is 86%, Mass Spectrometer Method (being called for short MS) (m/z): 331.9。
Embodiment 13-embodiment 22 compound 13～the preparation of compound 22
Compound 13～22 is prepared the most by the following method:
The method be given according to embodiment 12 and proportioning raw materials, wherein using different types of substrate is raw material, all with Diaminomaleonitrile carries out ring closure reaction, the most in various embodiments, selected raw material and obtain corresponding compound with And yield and Mass Spectrometer Method result as shown in table 2 below.
Table 2
The preparation of embodiment 23 aforesaid compound C001
In 100mL there-necked flask, add compound 1 (2.83g, 0.01mol), carbazole (2.0g, 0.012mol), the tert-butyl alcohol Sodium (1.92g, 0.02mol), palladium (0.044g, 0.0002mol), tri-butyl phosphine (0.081g, 0.0004mol) and adjacent two Toluene (30g), is warming up to system backflow, after insulation reaction 8h, is cooled to 25 DEG C, adds 20g deionized water, stirring afterwards 10min, then separatory, collect organic facies, then sucking filtration, after sucking filtration, to filtrate desolventizing, it is thus achieved that crude product, then use silicagel column Chromatography purification crude product, wherein eluant is ethyl acetate, re-uses chemical gas-phase deposition system distillation further to crude product afterwards Purifying, wherein sublimation temperature is 320 DEG C, and final acquisition 1.7g compound C001, being computed yield is 46%.
Through high resolution mass spectrum, ESI source, after positive ion mode detection, the molecular formula of compound C001 is C26H15N3, detected value It is 369.1268, and theoretical value 369.1266；It addition, compound C001 is after elementary analysis, detects and obtain C: 84.54%, H:4.11%, N:11.35%, theoretical value C:84.53%, H:4.09%, N:11.37%.
The preparation of the part of compounds in embodiment 24-embodiment 61 compound C003～compound C235
Part of compounds in compound C003～compound 235 is prepared the most by the following method:
The method be given according to embodiment 23 and proportioning raw materials, carry out C-N coupling reaction, the simply kind of feed change Class, the most in various embodiments, it is thus achieved that corresponding compound structure, its corresponding molecular formula, prepare the yield of compound And high resolution mass spectrum and elementary analysis testing result are as shown in Table 3 below.
Table 3
Note: above-mentioned table 3 Wave line represents the position that C-N key generates.
The preparation of embodiment 62 compound C265
In 100mL there-necked flask, add compound 7 (3.62g, 0.01mol), carbazole (4.0g, 0.024mol), the tert-butyl alcohol Sodium (3.85g, 0.04mol), palladium (0.088g, 0.0004mol), tri-butyl phosphine (0.16g, 0.0008mol) and adjacent two Toluene (40g), is warming up to backflow, after insulation reaction 16h, is cooled to 25 DEG C, adds 20g deionized water afterwards, stirs 10min, Separatory again, collects organic facies, then sucking filtration afterwards, then by filtrate desolventizing, it is thus achieved that crude product, then use silica gel column chromatography purification Crude product, wherein eluant is ethyl acetate, is finally using chemical gas-phase deposition system further sublimation purification crude product, Qi Zhongsheng China's temperature is 350 DEG C, it is thus achieved that 2.9g compound C265, being computed yield is 54%.
Through high resolution mass spectrum, ESI source, after positive ion mode detection, the molecular formula of compound C265 is C38H22N4, detected value It is 534.1849, and theoretical value 534.1844；It addition, compound C265 is after elementary analysis, detects and obtain C: 85.34%, H:4.19%, N:10.47%, and theoretical value C:85.37%, H:4.15%, N:10.48%.
The preparation of the part of compounds in embodiment 63-embodiment 86 compound C266～compound C372
Part of compounds in compound C266～compound C372 is prepared the most by the following method:
The method be given according to embodiment 62 and proportioning raw materials, carry out C-N coupling reaction, the simply kind of feed change Class, the most in various embodiments, it is thus achieved that corresponding compound structure, its corresponding molecular formula, prepare the yield of compound And high resolution mass spectrum and elementary analysis testing result are as shown in Table 4 below.
Table 4
Note: above-mentioned table 4 Wave line represents the position that C-N key generates.
The preparation of embodiment 87 compound C013
In 100mL there-necked flask, add compound 1 (2.83g, 0.01mol), 4-(9H-carbazole) phenylboric acid (3.44g, 0.012mol), potassium carbonate (5.5g, 0.04mol), palladium (0.088g, 0.0004mol), triphenylphosphine (0.21g, 0.0008mol), toluene (40g) and deionized water (15g), system is warming up to backflow, after insulation reaction 16h, is cooled to 25 DEG C, then separatory, regather organic facies, afterwards sucking filtration, collect filtrate, desolventizing, it is thus achieved that crude product, then use silica gel column chromatography Purification crude product, wherein eluant is ethyl acetate, finally uses chemical gas-phase deposition system further sublimation purification crude product, wherein Sublimation temperature is 340 DEG C, it is thus achieved that 1.9g compound C013, is computed yield 43%.
Through high resolution mass spectrum, ESI source, after positive ion mode detection, compound C013 molecular formula is C32H19N3, detected value is 445.1573, and theoretical value 445.1579；It addition, compound C013 is after elementary analysis, detects and obtain C:86.23%, H: 4.29%, N:9.48%, and theoretical value C:86.27%, H:4.30%, N:9.43%.
The preparation of the part of compounds in embodiment 88-embodiment 138 compound C014～compound C239
Part of compounds in compound C014～compound 239 is prepared the most by the following method:
The method be given according to embodiment 87 and proportioning raw materials, carry out C-C coupling reaction, the simply kind of feed change Class, the most in various embodiments, it is thus achieved that corresponding compound structure, its corresponding molecular formula, prepare the yield of compound And high resolution mass spectrum and elementary analysis testing result are as shown in Table 5 below.
Table 5
Note: above-mentioned table 5 Wave line represents the position that C-C key generates.
The preparation of embodiment 139 compound C269
In 250mL there-necked flask, add compound 7 (3.62g, 0.01mol), 4-(9H-carbazole) phenylboric acid (6.9g, 0.024mol), potassium carbonate (11g, 0.08mol), palladium (0.088g, 0.0004mol), triphenylphosphine (0.21g, 0.0008mol), toluene (80g) and deionized water (35g), be warming up to backflow, after insulation reaction 28h, be cooled to 25 DEG C, then divide Liquid, collects organic facies, then sucking filtration afterwards, collects filtrate, desolventizing, it is thus achieved that crude product, re-uses silica gel column chromatography purification crude product, Wherein eluant is ethyl acetate, final utilization chemical gas-phase deposition system further sublimation purification crude product, wherein sublimation temperature Being 370 DEG C, final acquisition 2.7g compound C269, being computed yield is 39%.
Through high resolution mass spectrum, ESI source, after positive ion mode detection, the molecular formula of compound C269 is C50H30N4, detected value It is 686.2476, and theoretical value 686.2470；It addition, compound C269 is after elementary analysis, detects and obtain C: 87.46%, H:4.41%, N:8.13%, and theoretical value C:87.44%, H:4.40%, N:8.16%.
The preparation of the part of compounds in embodiment 140-embodiment 151 compound C270～compound C329
Part of compounds in compound C270～compound C329 is prepared the most by the following method:
The method be given according to embodiment 139 and proportioning raw materials, carry out C-C coupling reaction, the simply kind of feed change Class, the most in various embodiments, it is thus achieved that corresponding compound structure, its corresponding molecular formula, prepare the yield of compound And high resolution mass spectrum and elementary analysis testing result are as shown in Table 6 below.
Table 6
Note: above-mentioned table 6 Wave line represents the position that C-C key generates.
The preparation of embodiment 152 compound 27
The preparation of compound 23: in 1L there-necked flask, add 5-bromine acenaphthenequinone (26.1g, 0.1mol), 2,3-diaminostilbene, 4-butanediol (14.4g, 0.12mol) and glacial acetic acid (300mL), be warming up to backflow, then in air atmosphere, insulation reaction 18h, is down to room temperature afterwards, then after being poured into by reactant liquor in the deionized water of 1000mL, stirs 0.5h, then sucking filtration, then select 500mL deionized water drip washing filter cake, then select 150mL dehydrated alcohol drip washing filter cake, collect filter cake, it is thus achieved that compound 23 is 32.8g, being computed yield is 95.6%, and MS (m/z) detected value is 342.1.
The preparation of compound 24: in 500mL there-necked flask, adds compound 23 (32.5g, 0.095mol), manganese dioxide (35g, 0.4mol) and 1,2-dichloroethanes (300g), it is warming up to backflow, insulation reaction 32h, is cooled to 25 DEG C afterwards, then takes out Filter, collects filtrate, sloughs solvent, it is thus achieved that 22.4g compound 24, and being computed yield is 70%, and MS (m/z) detected value is 337.9.
The preparation of compound 25: in 500mL there-necked flask, adds compound 24 (22.2g, 0.066mol) and oxolane (120g), then it is cooled to 5 DEG C, then by oxammonium hydrochloride. (11.2g, 0.16mol), sodium acetate (13.1g, 0.16mol) is dissolved in In 140g deionized water, being then added drop-wise in there-necked flask, in controlling bottle, temperature is less than 25 DEG C, after dropping in 0.5 hour, 20 Insulation reaction 3 hours at DEG C, are warming up to 60 DEG C afterwards, and then insulation reaction 1 hour is cooled to 25 DEG C, is slowly fallen by reactant liquor Enter in 500mL deionized water, stir 1h, then sucking filtration afterwards, then select deionized water drip washing to neutral, collect filter cake, dry, Obtaining compound 25 is 23g, and being computed yield is 94%, and MS (m/z) detected value is 368.1.
The preparation of compound 26: in 500mL there-necked flask, adds compound 25 (22.5g, 0.061mol) and oxolane (150g), system is cooled to 15 DEG C, more chloro-for N-succimide (being called for short NCS) (16g, 0.12mol) is dissolved in 80g N, Among dinethylformamide (DMF), the most slowly instilling in there-necked flask, keeping reaction temperature is 25～28 DEG C, dropping in 2 hours After complete (when reaction causes, very exothermic), insulation reaction 2 hours at 25 DEG C, stopped reaction, stand-by.
The preparation of compound 27: in 500mL there-necked flask, add thiourea (10g, 0.133mol), triethylamine (14g, 0.133mol) with oxolane (55g), start stirring, be then slowly added dropwise the reactant liquor of compound 26 prepared by previous step, protect Hold reaction temperature and be less than 30 DEG C, after dropping in 1 hour, at 25 DEG C, be incubated 3 hours, then sucking filtration, collect filter cake, it is thus achieved that thick Product, re-uses silica gel column chromatography purifying crude product, and wherein eluant is ethyl acetate, it is thus achieved that compound 27 is 18.9g, through meter Calculating yield is 78%, MS (m/z) detected value 395.9.
The preparation of embodiment 153 compound 28
According to the method be given in embodiment 152 and proportioning raw materials, simply with 5,6-dibromo acenaphthenequinone is raw material, is prepared into To compound 28 be 8.2g, MS (m/z) detected value be 475.8.
The preparation of embodiment 154 compound C081
In 100mL there-necked flask, add compound 27 (1.58g, 0.004mol), carbazole (0.83g, 0.005mol), CuI (0.19g, 0.001mol), Phen (0.36g, 0.002mol), potassium carbonate (1.38g, 0.01mol) and o-dichlorohenzene (32g), system is warming up to 150 DEG C, after insulation reaction 32h, is down to room temperature, add toluene 50mL, use 20mL to go afterwards Ionized water washing organic facies twice, then separatory, collect organic facies, then the desolventizing that reduces pressure, it is thus achieved that crude product, select silica gel column chromatography Purification crude product, wherein eluant is the mixed solvent of ethyl acetate and dichloromethane, ethyl acetate and the volume ratio of dichloromethane For for ethyl acetate: dichloromethane=2:1, it is thus achieved that compound C081, re-use chemical gas-phase deposition system and distil further and carry Pure compound C081, wherein sublimation temperature is 310 DEG C, it is thus achieved that 0.9g compound C081, and being computed yield is 47%.
Through high resolution mass spectrum, ESI source, positive ion mode detects, molecular formula C of compound C08128H13N5S2, detected value is 483.0618, and theoretical value 483.0612；It addition, compound C081 is after elementary analysis, detects and obtain C:69.54%, H: 2.72%, N:14.44%, S:13.30%, and theoretical value C:69.55%, H:2.71%, N:14.48%, S:13.26%.
The preparation of the part of compounds in embodiment 155-embodiment 158 compound C089～compound C283
Part of compounds in compound C089～compound C283 is prepared the most by the following method:
The method be given according to embodiment 154 and proportioning raw materials, carry out C-N coupling reaction, the simply kind of feed change Class, the most in various embodiments, it is thus achieved that corresponding compound structure, its corresponding molecular formula, prepare the yield of compound And high resolution mass spectrum and elementary analysis testing result as shown in table 7 below.
Table 7
Note: above-mentioned table 7 Wave line represents the position that C-N key generates.
The preparation of embodiment 159 compound C093
In 50mL there-necked flask, add compound 27 (1.58g, 0.004mol), 4-(9H-carbazole) phenylboric acid (1.44g, 0.005mol), potassium carbonate (1.1g, 0.008mol), palladium (0.022g, 0.0001mol), triphenylphosphine (0.052g, 0.0002mol), toluene (28g) and deionized water (12g), after system is warming up to backflow, insulation reaction 16h, be cooled to afterwards 25 DEG C, then separatory, collect organic facies, then sucking filtration, collects filtrate, then desolventizing, it is thus achieved that crude product uses silica gel column chromatography to carry out Purification, wherein eluant is ethyl acetate, then uses the further sublimation purification of chemical gas-phase deposition system, wherein sublimation temperature Being 330 DEG C, it is thus achieved that 1.1g compound C093, being computed yield is 49%.
Through high resolution mass spectrum, ESI source, positive ion mode detects, molecular formula C of compound C09334H17N5S2, detected value is 559.0921, and theoretical value 559.0925；It addition, compound C093 is after elementary analysis, detects and obtain C:72.99%, H: 3.07%, N:12.49%, S:11.45%, and theoretical value C:72.97%, H:3.06%, N:12.51%, S:11.46%.
The preparation of the part of compounds in embodiment 160-embodiment 164 compound C099-compound C117
Part of compounds in compound C099～compound C117 is prepared the most by the following method:
The method be given according to embodiment 159 and proportioning raw materials, carry out C-C coupling reaction, the simply kind of feed change Class, the most in various embodiments, it is thus achieved that corresponding compound structure, its corresponding molecular formula, prepare the yield of compound And high resolution mass spectrum and elementary analysis testing result as shown in table 8 below.
Table 8
Note: above-mentioned table 8 Wave line represents the position that C-C key generates.
Data from above-mentioned table 1～table 8 are it is known that the present invention have successfully been obtained provided organic photoelectric material Material, i.e. organic photoelectrical material shown in formula I.
Embodiment two prepares organic electroluminescence device (may be simply referred to as device below)
In the following embodiment preparing organic electroluminescence device, used reagent material is as follows:
Anode: tin indium oxide (being called for short ITO) electro-conductive glass, hole mobile material: NPB,
Luminescent material: mCP, electron transport material: TPBI, electron injection material: LiF, wherein, NPB, mCP and TPBI Structural formula mention in the preamble, do not repeat them here.
Embodiment 165～the preparation of embodiment 231 device 165～231
Organic electroluminescence device is prepared the most by the following method:
A) anode is cleaned: clean ITO electro-conductive glass with deionized water, acetone, EtOH Sonicate respectively, each in above-mentioned solvent Ultrasonic cleaning 30 minutes, then processes 5 minutes in plasma cleaner；
B) vacuum evaporation hole mobile material NPB on the anode obtained in step a), it is thus achieved that hole transmission layer, thickness is 50nm；
C), on the hole transmission layer obtained in step b), vacuum evaporation includes the change prepared in previous embodiment one Compound and the luminescent material of mCP, it is thus achieved that luminescent layer, the thickness of luminescent layer is 30nm, wherein, compound: mCP=1:10 (W/W)；
D) on the luminescent layer obtained in step c), vacuum evaporation electron transport material TPBI, it is thus achieved that electron transfer layer, electricity The thickness of sub-transport layer is 30nm；
E) on the electron transfer layer obtained in step d), vacuum evaporation electron injection material LiF, it is thus achieved that electronics injects Layer, the thickness of electron injecting layer is 1nm；
F) on the electron injecting layer obtained in step e), vacuum evaporation negative electrode Al, the thickness of negative electrode is 100nm, it is thus achieved that Organic electroluminescence device.
Preparing in organic electroluminescence device above-mentioned, during vacuum evaporation, pressure is less than 1.0 × 10-3Pa。
The organic electroluminescence device prepared by above-mentioned preparation process, as shown in fig. 1, including anode 101, hole Transport layer 102, luminescent layer 103, electron transfer layer 104, electron injecting layer 105, negative electrode 106, wherein, hole transmission layer 102, send out Photosphere 103, electron transfer layer 104, electron injecting layer 105 are respectively positioned between negative electrode 106 and anode 101, on anode 101 successively It is stacked with hole transmission layer 102, luminescent layer 103, electron transfer layer 104 and electron injecting layer 105.
Test example
Japan is selected to open up the organic electroluminescent that above-described embodiment is prepared by general Kanggong department SR3 type spectroradiometer Device carries out following test, obtains opening bright voltage, maximum current efficiency and spectral color in each organic electroluminescence device.
In above-mentioned test example, detect obtained by each organic electroluminescence device open bright voltage, maximum current efficiency and Spectral color is as shown in Table 9 below.
Table 9
By above-mentioned table 9 as a result, it is possible to learn, organic photoelectrical material provided by the present invention can be applicable to organic electroluminescence and sends out In optical device.Additionally, by by the testing result of the device prepared in embodiment, it is also possible to learning, the present invention provides Organic photoelectrical material makes organic electroluminescence device obtain excellent performance, organic photoelectrical material conduct provided by the present invention The luminescent material of organic electroluminescence device uses so that device has bigger maximum current efficiency, and device is had Relatively low opens bright voltage, and meanwhile, device can send the visible ray of different colours, and spectral coverage is wider.
The announcement of book according to the above description, above-mentioned embodiment can also be carried out by those skilled in the art in the invention Suitable change and amendment.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to the present invention's Some modifications and changes should also be as falling in the scope of the claims of the present invention.

Claims (9)

1. an organic photoelectrical material, it is characterised in that shown in following formula I:
Wherein, R1And R2It is each independently selected from the one in hydrogen-based, cyano group, isothiocyano and phenyl, R3、R4、R5、R6、R7And R8 Being each independently selected from hydrogen-based, halogen and carbon number is 10～50 and containing the aromatic heterocycle of at least one in N, S, O One in base.
Organic photoelectrical material the most according to claim 1, it is characterised in that halogen is fluorine-based, chloro, bromo.
Organic photoelectrical material the most according to claim 1, it is characterised in that R1And R2Identical.
Organic photoelectrical material the most according to claim 1, it is characterised in that described aromatic heterocyclic radical is selected from following formula (1) ～one or more in the group shown in formula (21):
Wherein, R9And R10Be each independently selected from hydrogen-based, virtue that alkyl that carbon number is 1～10, carbon number are 6～10 Base, carbon number are the aryl amine of 6～20 and containing the one in N and annelated heterocycles base that carbon number is 12～20, R11Selected from hydrogen-based or alkyl that carbon number is 1～10, L selected from the arlydene that carbon number is 6～20, carbon number be 6～ One in the halo arlydene of 20 and sub-virtue cyano group, M selected from secondary aryl that carbon number is 6～20, the secondary aryl of halo with And secondary virtue cyano group in one, wherein, halogen atom is F, Cl, Br.
Organic photoelectrical material the most according to claim 4, it is characterised in that
R9And R10Be each independently selected from alkyl that carbon number is 1～6, carbon number be 6～8 aryl, carbon number be The aryl amine of 12～16 and containing N and annelated heterocycles base that carbon number is 12～16；
R11Selected from the alkyl that carbon number is 1～6；
L is selected from the one in the arlydene that carbon number is 6～12 and the fluoro arlydene that carbon number is 6～12；
M is selected from the secondary aryl that carbon number is 6～12.
Organic photoelectrical material the most according to claim 4, it is characterised in that
R9And R10The one being each independently selected from following radicals: methyl, the tert-butyl group, phenyl, hexichol amido and carbazyl,
R11One in following radicals: methyl and the tert-butyl group,
L one in following radicals:
M is
Organic photoelectrical material the most according to claim 1, it is characterised in that R3、R4、R5、R6、R7And R8Select independently of one another From fluorine-based and in following radicals one:
8. an organic electroluminescence device, it is characterised in that include negative electrode, anode and luminescent layer, described luminescent layer position Between described anode and described negative electrode, wherein said luminescent layer is by the organic photoelectric material according to any one of claim 1～7 Material prepares.
Organic electroluminescence device the most according to claim 8, it is characterised in that also include that hole transmission layer, electronics pass Defeated layer and electron injecting layer, wherein, described hole transmission layer, described luminescent layer, described electron transfer layer and described electronics inject Layer is respectively positioned between described negative electrode and described anode, has been sequentially stacked described hole transmission layer, described luminescence on described anode Layer, described electron transfer layer and described electron injecting layer.
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CN108440424A (en) * 2018-04-10 2018-08-24 苏州大学 Acenaphthene and pyrazines derivatives and its application
CN109456276A (en) * 2018-10-22 2019-03-12 武汉华星光电半导体显示技术有限公司 Dark red photo-thermal activation delayed fluorescence material and its synthetic method, electroluminescent device
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CN110746364A (en) * 2018-12-06 2020-02-04 广州华睿光电材料有限公司 Acenaphthenequinone organic compound and application thereof
CN109988559A (en) * 2019-04-25 2019-07-09 武汉华星光电半导体显示技术有限公司 Thermal activation delayed fluorescence material and organic light-emitting diode (OLED) display apparatus

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