CN108017645A - A kind of perimidine derivative and its application - Google Patents

A kind of perimidine derivative and its application Download PDF

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Publication number
CN108017645A
CN108017645A CN201610965924.4A CN201610965924A CN108017645A CN 108017645 A CN108017645 A CN 108017645A CN 201610965924 A CN201610965924 A CN 201610965924A CN 108017645 A CN108017645 A CN 108017645A
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layer
derivative
organic
compound
heteroaryl
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范洪涛
李之洋
张伟
邵爽
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Abstract

The present invention relates to a kind of novel organic compound, more particularly to a kind of perimidine derivative, and further disclose it and be used to prepare the application of organic electroluminescence device.One kind perimidine derivative disclosed by the invention has good carrier transport, it can be used as electron transport material and phosphorescent light body material in OLED device, device test data is shown, it is used as the electron transport material in organic electroluminescence device using derivative of the present invention, since it is with good electron injection, high mobility and with high triplet energy level, device can thus be significantly reduced and play bright and operating voltage, and play the role of improving device efficiency；It is used as the phosphorescent light body material in organic electroluminescence device using derivative of the present invention, since it has balanced hole and electronic transmission performance, and be conducive to significantly reduce a bright and operating voltage for device and with high triplet with suitable band gap, be conducive to exciton energy effectively passing to phosphorescent coloring, play the role of improving device efficiency.

Description

A kind of perimidine derivative and its application
Technical field
The present invention relates to a kind of novel organic compound, more particularly to a kind of perimidine derivative, one is gone forward side by side Step discloses it and is used to prepare the application of organic electroluminescence device.
Background technology
Electro optical phenomenon most early in 20th century the '30s be found, initial luminescent material is ZnS powder, and thus LED technology has been developed, has been widely applied to now on energy-conserving light source.And organic electroluminescent phenomenon is Pope in 1963 etc. What people had found earliest, they have found that the single layer crystal of anthracene under the driving of more than 100V voltages, can send faint blue light.Directly Bi-layer devices are made in organic fluorescent dye by doctor Deng Qingyun to Kodak in 1987 et al. in a manner of vacuum evaporation, are being driven Under dynamic voltage of the voltage less than 10V, external quantum efficiency has reached 1% so that electroluminescent organic material and device are provided with reality With the possibility of property, the research of OLED material and device has been promoted significantly from this.
Display of organic electroluminescence (hereinafter referred to as OLED) has from main light emission, low-voltage direct-current driving, all solidstate, regards Angular width, light-weight, composition and a series of advantages such as technique is simple, compared with liquid crystal display, display of organic electroluminescence Backlight is not required, visual angle is big, and power is low, and up to 1000 times of liquid crystal display, it manufactures cost and is but less than its response speed The liquid crystal display of equal resolution ratio, therefore, organic electroluminescence device has broad application prospects.
As OLED technology is illuminating and showing the continuous propulsion in two big fields, people grind for its efficient organic material Study carefully and focus more on, it is excellent with various organic materials that the organic electroluminescence device of an excellent in efficiency long lifespan is typically device architecture Change collocation as a result, and often the effect of material it is more notable, it may be said that the performance of material is the basic of OLED technology.OLED is led Organic material in domain mainly includes：Hole-injecting material, hole mobile material, hole barrier materials, electron injection material, electricity Sub- transmission material, electron-blocking materials and light emitting host material and light-emitting guest (dyestuff) etc..
The electron transport material that tradition uses in electroluminescent device is Alq3, but Alq3Electron mobility than relatively low (about 10-6cm2/ Vs), it have impact on the electronic transmission performance of electroluminescent device.In order to obtain high performance electric transmission material Material, it is desirable to which material has high electron mobility, good film forming, high thermal stability, and suitable HOMO and LUMO Energy level is to match luminescent layer material of main part energy level, to realize good electron injection and hole barrier function.LG chemistry exists A series of derivative of pyrenes is reported in CN101003508A, electric transmission and injection material are used as in electroluminescence device, is carried The high luminous efficiency of device.Cao Yong et al. synthesizes FFF-Blm4 (J.Am.Chem.Soc.；(Communication)； 2008；130(11)；3282-3283) as electric transmission and layer material is injected (with Ba/Al and individually by the use of Al as compared with cathode Compared with), electron injection and the transmission of device are significantly improved, improves electroluminescence efficiency.Kodak is (open in United States Patent (USP) Number US 2006/0204784 and US 2007/0048545) in, mixed electronic transport layer is mentioned, using a kind of low lumo energy Material is formed with doping such as the electron transport material of another low bright voltage and other materials such as metal materials.Based on this mixed The device of electron transfer layer is closed, is improved device efficiency, but adds the complexity of device fabrication, is unfavorable for reducing OLED costs.
Therefore, the defects of current electron transport material mobility is low, and triplet is not high how is overcome, exploitation stablizes, Efficiently, high mobility and the electron transport material with high triplet energy level, play bright and operating voltage for reducing device, carry High device efficiency, extending device lifetime and reducing OLED device complex process degree has critically important actual application value.
Red, green light material is commercialized at present and generally uses the phosphor material containing heavy metal, in order to fully play phosphorescence dye The high efficiency of material, as phosphorescent light body material it is necessary to have the triplet higher than corresponding phosphorescent light-emitting materials, to ensure to fill The energy transfer divided realizes high luminous efficiency, while needs and adjacent electronics and hole transport layer material phase to luminescent material The energy level matched somebody with somebody will also have the carrier transport ability of relative equilibrium to facilitate the injection of carrier.Common phosphorescence host Material C BP (special open 2001-313178 publications), has a good hole transport performance, and in terms of electronic transmission performance compared with Difference, causes carrier transport unbalanced.And using TAZ as material of main part (special open 2002-352957 publications) then on the contrary, having Electron transport ability well, but cavity transmission ability is poor, can not equally realize the carrier transport of equilibrium.Therefore open Material of the hair with relatively balanced electronics and hole transport performance, it will be obviously improved to the efficiency of phosphorescent devices.
Therefore, device operating voltages height and current density and electricity made of existing organic electroluminescent compounds how are overcome The defects of efficiency is low is flowed, exploitation is with balanced carrier transmission performance and avoids the phosphorescence master of efficiency roll-off under high illumination Body material, so that reducing device plays bright and operating voltage, improves device efficiency, extends device lifetime, have critically important reality Meaning.
The content of the invention
For this reason, the technical problems to be solved by the invention are to provide a kind of perimidine compound and its derivative Thing, and further provide the application that said derivative is used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field, specifically, the derivative In display of organic electroluminescence, it is used as phosphorescent light body material, electron transport material.
In order to solve the above technical problems, perimidine derivative of the present invention, it is characterised in that have such as Structure shown in lower general formula (C)：
Wherein, Ar1With Ar2Differ, it is independent of each other to be selected from halogen, substituted or unsubstituted C1~C30Alkyl, substitution or Unsubstituted C3~C30Cycloalkyl, substituted or unsubstituted C2-C30Heterocyclylalkyl, substitution or unsubstituted C6~C30Arylamino Or heteroaryl amino, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C2~C30Heteroaryl；
L1、L2It is independent of each other to be selected from singly-bound, substitution or unsubstituted C6~C30Arylamino or heteroaryl amino, substitution Or unsubstituted C6~C30Aryl, substituted or unsubstituted C2~C30Heteroaryl；
Hetero atom in the heteroaryl or the heteroaryl amino is to be at least one selected from B, N, O, S, P, P (=O), Si With the hetero atom of Se.
Preferably, the substituted or unsubstituted alkyl is selected from C1-C10Alkyl, and more preferably from C1-C6Alkyl；
The substituted or unsubstituted cycloalkyl is selected from C3-C6Cycloalkyl；
The substituted or unsubstituted arylamino or heteroaryl amino include ammonia diaryl base, two (miscellaneous) arylaminos, Triaryl amino or three (miscellaneous) arylaminos；
The substituted or unsubstituted Heterocyclylalkyl, which is selected from, has C3-C10A ring skeleton atom and comprising at least one described Heteroatomic Heterocyclylalkyl；
The substituted or unsubstituted aryl is selected from C6-C20Aryl；
The substituted or unsubstituted heteroaryl is selected from C2-C20Heteroaryl.
More preferably, the C1-C30Alkyl include methyl, ethyl, n-propyl, isopropyl, normal-butyl, n-hexyl, just pungent Base, isobutyl group or the tert-butyl group；
The C3-C30Cycloalkyl include cyclopropyl, cyclobutyl, cyclopenta and/or cyclohexyl；
The C6-C30Arylamino or heteroaryl amino include diphenylamino, phenyl napthyl amino, tri- phenylaminos of 4-, Tri- phenylaminos of 3-, 4- [N- phenyl-N- (dibenzofurans -3- bases)] phenyl aminos or 4- [N- phenyl-N- (dibenzothiophenes -3- Base)] phenyl amino；
The C2-C30Heterocyclylalkyl includes tetrahydrofuran, pyrrolidines and/or thiophane；
The C6-C30Aryl include phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and its Derivative, fluoranthene base, triphenylene, pyrenyl, base,Base and aphthacene base；And it is highly preferred that the xenyl selects 2- to join Phenyl, 3- xenyls and 4- xenyls, the terphenyl include p- terphenyl -4- bases, p- terphenyl -3- bases, p- Terphenyl -2- bases, m- terphenyl -4- bases, m- terphenyl -3- bases and m- terphenyl -2- bases；The naphthyl is In the group that 1- naphthyls and 2- naphthyls are formed；The anthryl is in the group being made of 1- anthryls, 2- anthryls and 9- anthryls；Institute Fluorenyl is stated in the group being made of 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls and 9- fluorenyls；The fluorenyl derivative choosing Freely 9,9 '-dimethyl fluorene, 9, in the group that 9 '-spiral shell, two fluorenes and benzfluorene are formed；
The C2-C30Heteroaryl include thiazole, benzothiazole, phenanthro- imidazoles, phenanthro- benzothiophene benzimidazole, dislike Azoles, oxadiazoles, triazole, pyridine, pyrimidine, triazine, evil boron heterocycle, quinoline, isoquinolin, quinoxaline, quinazoline, benzoxazoles, phenanthrene And oxazole, phenanthro- thiazole, bipyridyl, phenanthridines, phenanthroline, imidazopyridine, imidazopyrimidine, phenoxazine, phenthazine, dimethyl Acridan, the miscellaneous benzene of 1,2,5,10- tetrahydrochysene dibenzo boron, the miscellaneous benzene of 10,10- dimethyl -5,10- tetrahydrochysene dibenzo boron, 4- biphenyl Acyl group, furyl, thienyl, pyrrole radicals, benzofuranyl, benzothienyl, isobenzofuran-base, indyl, dibenzo furan Mutter base, dibenzothiophene, carbazyl and its derivative, benzodioxole group；And the carbazole radical derivative can To include but not limited to 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole, indolocarbazole, N- Phenylindoles And at least one of carbazole, benzofuran and carbazole.
Optimal, the derivative preferably is selected from structure shown in following C1-C64：
The invention also discloses the perimidine derivative to be used to prepare answering for organic electroluminescence device With.
The perimidine derivative is used as electron transport material and/or phosphorescent light body material.
The invention also discloses a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；
The electron transport material of the electron transfer layer includes at least one perimidine derivative material Material.
The invention also discloses a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；
The phosphorescent light body material of the organic luminous layer includes at least one perimidine derivative material Material.
The invention also discloses a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；
The electron transport material of the electron transfer layer includes at least one perimidine derivative material Material；And
The phosphorescent light body material of the organic luminous layer includes at least one perimidine derivative material Material.
The molecular system of derivant material of the present invention based on the structure of perimidine containing azo-cycle, have it is high Triplet, and the presence of carbonyl causes molecule to have higher electron affinity, and in addition precursor structure has flatness, Its conjugacy is fine, by Gauss quantum chemical method the results show that the HOMO energy levels of parent molecule and the electron cloud of lumo energy are equal It is distributed in evenly on whole skeleton, thus (triplet of its precursor structure is about with very excellent carrier transport For 2.75eV).And by select with specific electron property group, can significantly improve material HOMO energy levels and Lumo energy, makes it have different carrier transports, so as to fulfill different function layer uses, can realize be used as respectively The purpose of electron transport layer materials and phosphorescent light body material (the HOMO energy levels of parent molecule and the electricity of lumo energy molecular orbit Sub- cloud distribution map is referring to attached drawing 1-2).In addition different structure and the substituent of size can also play point for adjusting material molecule Son amount and symmetry, can further improve the carrier transport and film forming stability of material.
One kind perimidine derivative disclosed by the invention, the good carrier transport of the compound, this To invent the derivative and can be used as electron transport material and phosphorescent light body material in OLED device, device test data is shown, It is used as the electron transport material in organic electroluminescence device using derivative of the present invention, since it is with good electronics Injection, transporting, have high triplet energy level and high mobility, it is thus possible to and significantly reduce device and play bright and operating voltage, And play the role of improving device efficiency.
In addition the compound of the present invention with electron substituent may be used as the phosphorescence host in OLED device Material, due to material possessed balanced and high bipolarity carrier transmission performance in itself, can effectively reduce device Efficiency roll-off under high illumination, and play the effect for extending device operational lifetime.
Brief description of the drawings
In order to make the content of the present invention more clearly understood, the specific embodiment below according to the present invention and combination Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the Cloud Distribution figure of the HOMO energy level molecular orbits of the parent molecule of the compounds of this invention；
Fig. 2 is the Cloud Distribution figure of the lumo energy molecular orbit of the parent molecule of the compounds of this invention.
Embodiment
Below with reference to following embodiments be described in detail organic electroluminescent compounds and preparation method thereof of the present invention with And the preparation method and luminosity of the luminescent device comprising the compound.
Various chemicals such as petroleum ether, ethyl acetate, tetrahydrofuran, n-hexane, toluene, second used in the present invention Acid, dichloromethane, DMF, 1,8- dinaphthylamine, N, the bromo- 2- iodonitrobenzenes of N'- carbonyl dimidazoles, 4-, sodium tert-butoxide, three (two benzal Benzylacetone) two palladiums, tetra-triphenylphosphine palladium, tri-butyl phosphine toluene solution, palladium, isoamyl nitrite, zinc powder, sodium sulphate etc. Chemical products it can be commercially available at home.
The synthesis of main intermediate
The synthesis of 1. intermediate M1 of synthetic example：
1,8- dinaphthylamines (50g, 0.316mol) and 500 milliliters of dichloromethane are added into 3 liters of there-necked flasks, is added dropwise at room temperature The mixed solution of N, N'- carbonyl dimidazoles (56.4g, 0.348mol) and 1200 milliliters of dichloromethane.After adding, room temperature reaction 2 Filtered after hour, with eluent methylene chloride filter cake, obtain compound M1 (54.5g, 94%).
The synthesis of 2. intermediate M2 of synthetic example：
By the bromo- 2- iodonitrobenzenes (65.6g, 0.2mol) of intermediate M1 (18.4g, 0.1mol), 4-, sodium tert-butoxide Two palladium (0.92g, 0.001mol) of (28.5g, 0.3mol), three (dibenzalacetone), 10% tri-butyl phosphine toluene solution (368 milliliters) mixing of (6.06g, 0.003mol) and toluene, when stirring 24 is small under reflux conditions, after reaction, are cooled to Room temperature, adds 500 milliliters of pure water, and organic layer is extracted with ethyl acetate, is spin-dried for after the drying of organic phase anhydrous sodium sulfate, then carries out Post separation (eluent：Dichloromethane/n-hexane), obtain compound M2 (41.5g, 71.1%).
The synthesis of 3. intermediate M3 of synthetic example：
By intermediate M2 (58.4g, 0.1mol), 580ml ethanol, iron powder (4.3g, 1mol), 290ml saturated ammonium chloride water Solution, temperature rising reflux reaction 5h, point board monitoring reaction are completed, and filtering, filter cake is eluted with ethyl acetate, organic after filtrate liquid separation Mutually it is spin-dried for, obtains intermediate M3 (48.2g, yield 91.9%)
The synthesis of 4. intermediate M4 of synthetic example：
Intermediate M3 (5.2g, 10mmol) is dissolved in 16ml acetic acid, adds 1g copper powders, stirring is cooled to 5-10 DEG C, uses Acetic acid (8ml) dissolving isoamyl nitrite (3.9g, 33mmol), is slowly added dropwise into system, is stirred at room temperature after being added dropwise, point To the reaction was complete, liquid separation, organic phase is washed one time with aqueous sodium carbonate, is dried with anhydrous sodium sulfate, is spin-dried for laggard for board monitoring Row column chromatography (eluent：Dichloromethane/petroleum ether), obtain product intermediate M4 (3.0g, yield 62.0%).1H NMR (500MHz, Chloroform) δ 8.87 (d, J=1.6Hz, 1H), 8.11-8.03 (m, 2H), 8.00 (d, J=7.5Hz, 1H), 7.63 (d, J=7.5Hz, 1H), 7.50-7.36 (m, 3H), 7.29 (d, J=7.5Hz, 1H), 7.08 (dd, J=7.5,1.4Hz, 1H).
The synthesis of synthetic example 5.C1 compounds：
Nitrogen protection under, by intermediate M4 (4.90g, 10mmol), 9,9'- spiral shells two [9H- fluorenes] -2- boric acid (3.6g, 10mmol), Pd (PPh3) 4 (0.125g, 0.1mmol), potassium carbonate (3.45g, 25mmol), toluene (80mL) and EtOH (40mL) Mixed with distilled water (20mL), when then stirring reaction 2 is small under reflux.After the completion of reaction, enter water quenching go out ethyl acetate extraction, Organic phase concentrates, then with toluene ethanol (1:1) recrystallize, compound C1-a (6.0g, 82.6%) is obtained after drying.
Under nitrogen protection, C1-a (6.0g, 8.26mmol) is added in 60mlTHF, is cooled to -78 DEG C, starts to be added dropwise N-Buli (4ml, 10mmol), 30min is kept the temperature after being added dropwise to complete, by 2- chlorine [9,10-d] thiazole luxuriant and rich with fragrance (2.7g, 10mmol) 40mlTHF solution is added dropwise in reaction bulb, after gradually recover room temperature reaction, add water quenching go out ethyl acetate extraction, it is organic The mutually compound C1 5.4g of concentration dimethylbenzene recrystallization, yield 74.0%.1H NMR(500MHz,Chloroform)δ8.98 (dd, J=14.2,3.7Hz, 2H), 8.77 (d, J=2.9Hz, 1H), 8.54 (d, J=3.1Hz, 1H), 8.09 (ddd, J= 15.9,9.5,3.3Hz, 4H), 8.00 (d, J=15.0Hz, 1H), 7.95-7.82 (m, 4H), 7.77 (dt, J=11.5, 5.8Hz, 1H), 7.74-7.54 (m, 10H), 7.47 (ddd, J=24.0,15.0,2.9Hz, 2H), 7.40-7.17 (m, 6H), 7.08 (dd, J=15.0,3.0Hz, 1H)
The synthesis of synthetic example 6.C2 compounds：
Under nitrogen protection, by intermediate M4 (4.90g, 10mmol), 2- dibenzothiophenes boric acid (2.3g, 10mmol), Pd (PPh3) 4 (0.125g, 0.1mmol), potassium carbonate (3.45g, 25mmol), toluene (80mL) and EtOH (40mL) and distilled water (20mL) is mixed, when then stirring reaction 2 is small under reflux.After the completion of reaction, enter water quenching and go out ethyl acetate extraction, organic phase is dense Contracting, then with toluene ethanol (1:1) recrystallize, compound C2-a (5.1g, 85.3%) is obtained after drying.
Nitrogen protection under, by intermediate C2-a (5.1g, 8.53mmol), (4- (diphenylamines) phenyl) boric acid (2.9g, 10mmol), Pd (PPh3) 4 (0.125g, 0.1mmol), potassium carbonate (3.45g, 25mmol), toluene (80mL) and EtOH (40mL) Mixed with distilled water (20mL), when then stirring reaction 2 is small under reflux.After the completion of reaction, be down to room temperature, filter, filter cake according to It is secondary to be eluted with water and toluene, then recrystallized with dimethylbenzene, compound C2 (5.1g, 78.2%) is obtained after drying.1H NMR (500MHz, Chloroform) δ 9.21 (d, J=3.0Hz, 1H), 8.55 (d, J=2.9Hz, 1H), 8.49-8.39 (m, 2H), 8.12 (dd, J=15.0,2.9Hz, 1H), 7.99 (dd, J=15.0,6.0Hz, 2H), 7.87 (ddd, J=15.0,5.5, 3.1Hz, 2H), 7.71 (d, J=15.0Hz, 1H), 7.67-7.42 (m, 7H), 7.41-7.16 (m, 7H), 7.13-6.92 (m, 7H).
The synthesis of synthetic example 7.C3 compounds：
Nitrogen protection under, by intermediate M4 (4.90g, 10mmol),7H- benzos [C] carbazole(2.17g, 10mmol), Pd2 (DBA)3(0.06g, 0.1mmol), sodium tert-butoxide (2.4g, 25mmol), tri-butyl phosphine (0.06,0.2mmol), toluene (80mL), when then stirring reaction 4 is small under reflux.After the completion of reaction, enter water quenching go out ethyl acetate extraction, organic phase concentration, Then toluene ethanol (1 is used:1) recrystallize, compound C3-a (5.2g, 82.4%) is obtained after drying.
Nitrogen protection under, by intermediate C3-a (5.2g, 8.24mmol), N- phenyl carbazole -3- boric acid (2.9g, 10mmol), Pd (PPh3) 4 (0.125g, 0.1mmol), potassium carbonate (3.45g, 25mmol), toluene (80mL) and EtOH (40mL) Mixed with distilled water (20mL), when then stirring reaction 2 is small under reflux.After the completion of reaction, be down to room temperature, filter, filter cake according to It is secondary to be eluted with water and toluene, then recrystallized with dimethylbenzene, compound C3 (5.2g, 73.1%) is obtained after drying.1H NMR (500MHz, Chloroform) δ 8.75 (d, J=3.0Hz, 1H), 8.62 (d, J=3.1Hz, 1H), 8.54 (ddd, J=6.7, 6.0,4.0Hz, 3H), 8.24-8.13 (m, 1H), 7.99 (ddd, J=17.2,8.8,5.6Hz, 2H), 7.95-7.83 (m, 6H), 7.71 (d, J=15.0Hz, 2H), 7.67-7.35 (m, 14H), 7.25-7.03 (m, 6H)
The synthesis of synthetic example 8.C4 compounds：
The synthesis of C4 compounds is identical with synthetic example 6, and difference is 2- dibenzothiophenes boric acid, (4- (hexichol Amine) phenyl) boric acid is substituted for equivalent (3'- (3,5- diphenyl -4H-1,2,4- triazoles -4-yl)-[1,1'- xenyls] - 3- yls) phenyl boric acid, (4- (5- (tert-butyl group) -1,3,4- oxadiazoles -2- bases) phenyl) boric acid, obtain compound C4 (5.2g, 58%)1H NMR (500MHz, Chloroform) δ 9.09 (d, J=3.0Hz, 1H), 8.42 (d, J=2.9Hz, 1H), 8.35- 8.20 (m, 4H), 8.11 (ddd, J=5.1,4.6,2.5Hz, 2H), 8.04-7.82 (m, 4H), 7.76-7.56 (m, 6H), 7.55-7.40 (m, 11H), 7.30-7.20 (m, 2H), 7.08 (dd, J=15.0,3.0Hz, 1H), 1.35 (s, 9H)
Synthetic example 9.
Synthesis without synthetic example C5-C11 compounds is identical with synthetic example 6, and difference is 2- dibenzo thiophenes Fen boric acid, (4- (diphenylamines) phenyl) boric acid are substituted for the boric acid analog derivative of equivalent
The synthesis of synthetic example 10.C12 compounds：
The synthesis of C12 compounds is identical with synthetic example 7, difference be by7H- benzos [C] carbazoleIt is substituted for equivalentPhenthazine, N- phenyl carbazole -3- boric acid is substituted for (4- (3,5- dimethyl benzene) naphthalene -1- bases) boric acid of equivalent, changed Compound C12 (4.2g, 55.2%)1H NMR (500MHz, Chloroform) δ 9.08 (d, J=1.4Hz, 1H), 9.05-8.94 (m, 2H), 8.00 (d, J=7.5Hz, 1H), 7.87 (dd, J=7.5,1.4Hz, 1H), 7.76-7.55 (m, 5H), 7.45 (dt, J =3.0,1.4Hz, 2H), 7.39-7.30 (m, 4H), 7.30-7.13 (m, 8H), 7.08 (dd, J=7.5,1.4Hz, 1H), 7.02–6.91(m,2H),2.31(s,6H).
Synthetic example 11
Synthesis without synthetic example C3-C14 compounds is identical with synthetic example 6, and difference is 2- dibenzo thiophenes Fen boric acid, (4- (diphenylamines) phenyl) boric acid are substituted for the boric acid analog derivative of equivalent
The synthesis of synthetic example 12.C15 compounds：
The synthesis of C15 compounds is identical with synthetic example 5, and difference is to replace 9,9'- spiral shells two [9H- fluorenes] -2- boric acid Change equivalent into2- dibenzofurans boric acid, 2- chlorine [9,10-d] thiazole phenanthrene is substituted for equivalent2- chlorobenzene diozaioles, obtain To compound C15 (3.4g, 54.6%)1H NMR (500MHz, Chloroform) δ 9.33 (d, J=1.4Hz, 1H), 8.47 (d, J=1.4Hz, 1H), 8.29 (d, J=1.4Hz, 1H), 8.06-7.93 (m, 2H), 7.87 (dd, J=7.5,1.4Hz, 1H), 7.79-7.66 (m, 4H), 7.66-7.61 (m, 2H), 7.59 (d, J=7.5Hz, 1H), 7.54 (dd, J=7.5,1.4Hz, 1H), 7.52-7.47 (m, 1H), 7.44 (dt, J=11.1,5.6Hz, 1H), 7.42-7.34 (m, 3H), 7.31 (td, J=7.5, 1.5Hz, 1H), 7.08 (dd, J=7.5,1.4Hz, 1H)
The synthesis of synthetic example 13.C16 compounds：
The synthesis of C16 compounds is identical with synthetic example 5, and difference is to replace 9,9'- spiral shells two [9H- fluorenes] -2- boric acid Change equivalent (6,6,12,12- tetramethyl -6,12- indanes [1,2-b] fluorenes -2- bases) boric acid into, by 2- chlorine [9,10-d] thiazole Phenanthrene is substituted for equivalentThe chloro- 5- phenyl pyrimidines of 2-, obtain compound C16 (3.6g, 45.3%)1H NMR(500MHz, Chloroform) δ 9.38 (d, J=2.9Hz, 1H), 9.26 (s, 2H), 8.43 (dd, J=9.0,6.0Hz, 2H), 8.22 (d, J =3.1Hz, 1H), 8.09-7.80 (m, 6H), 7.76-7.55 (m, 4H), 7.55-7.18 (m, 9H), 7.08 (dd, J=15.0, 3.0Hz,1H),1.69(s,12H).
The synthesis of synthetic example 14.C17 compounds：
Under nitrogen protection, M4 (4.9g, 10mmol) is added in 60mlTHF, is cooled to -78 DEG C, start that n- is added dropwise Buli (4ml, 12mmol), 30min is kept the temperature after being added dropwise to complete, by chloro- 4, the 6- diphenyl -1,3,5-triazines of 2- (2.7g, 40mlTHF solution 10mmol) is added dropwise in reaction bulb, after gradually recover room temperature reaction, add water quenching and go out ethyl acetate Extraction, the compound C17-a 5.3g of organic phase concentration dimethylbenzene recrystallization, yield 82.1%.
Under nitrogen protection, C17-a (5.3g, 8.21mmol) is added in 60mlTHF, is cooled to -78 DEG C, starts to be added dropwise N-Buli (3.8ml, 10mmol), 30min is kept the temperature after being added dropwise to complete, by the chloro- 4- phenyl quinazolines azoles (2.0g, 8.21mmol) of 2- 40mlTHF solution is added dropwise in reaction bulb, after gradually recover room temperature reaction, add water quenching go out ethyl acetate extraction, it is organic The mutually compound C17 5.0g of concentration dimethylbenzene recrystallization, yield 78.5%.1H NMR(500MHz,Chloroform)δ9.73 (d, J=1.4Hz, 1H), 8.42-8.29 (m, 4H), 8.13 (dd, J=7.4,1.5Hz, 1H), 8.01 (dd, J=7.4, 4.5Hz, 2H), 7.87 (dd, J=7.5,1.4Hz, 1H), 7.79 (td, J=7.5,1.4Hz, 3H), 7.74-7.40 (m, 16H), 7.08 (dd, J=7.5,1.4Hz, 1H)
The synthesis of synthetic example 18.C25 compounds：
The synthesis of C25 compounds is identical with synthetic example 7, difference be by7H- benzos [C] carbazoleIt is substituted for equivalent 11- phenyl -11,12- indoline [2,3-a] carbazole, the 9- phenanthrene boric acid that N- phenyl carbazole -3- boric acid is substituted for equivalent, Obtain compound C12 (4.1g, 48.6%)1H NMR (500MHz, Chloroform) δ 9.15 (d, J=1.4Hz, 1H), 9.08 (dd, J=7.4,1.5Hz, 1H), 8.84 (dd, J=7.3,1.6Hz, 1H), 8.55 (dd, J=7.3,1.6Hz, 2H), 8.31- 8.23 (m, 2H), 8.20 (d, J=1.4Hz, 1H), 8.00 (d, J=7.5Hz, 1H), 7.90 (dt, J=7.2,1.4Hz, 1H), 7.75-7.55 (m, 11H), 7.51 (ddd, J=10.3,7.4,1.5Hz, 5H), 7.45 (dd, J=7.5,1.4Hz, 1H), 7.32 (dd, J=7.5,1.4Hz, 1H), 7.21-7.03 (m, 6H)
The synthesis of synthetic example 19.C28 compounds：
Nitrogen protection under, by intermediate M4 (4.90g, 10mmol), (3- (pyridin-4-yl) phenyl) boric acid (2.0g, 10mmol)、Pd(PPh3)4(0.125g, 0.1mmol), potassium carbonate (3.45g, 25mmol), toluene (80mL) and EtOH (40mL) Mixed with distilled water (20mL), when then stirring reaction 2 is small under reflux.After the completion of reaction, enter water quenching go out ethyl acetate extraction, Organic phase concentrates, then with toluene ethanol (1:1) recrystallize, compound C28-a (4.9g, 87.6%) is obtained after drying.
Under nitrogen protection, by C28-a (4.9g, 8.76mmol), isopropanol pinacol borate (1.9g, 10mmol) and THF (100ml) is mixed, and liquid nitrogen is down to -78 DEG C, and n-BuLi (5.3ml, 12mmol) is added dropwise, when insulation 1.5 is small after adding.Add Enter 100ml saturated aqueous ammonium chlorides and reaction, liquid separation is quenched, organic phase is spin-dried for after being dried with anhydrous sodium sulfate.Obtain intermediate C28-b 4.2g, dry stand-by, yield 78.0%.
Under nitrogen protection, zinc powder (1.63g, 25mmol) and THF (30ml) are mixed, 2 drop 1,2- Bromofumes is added, draws After hair, start the mixture of dropwise addition 2,2'- (propane -2,2- diyl) double (bromobenzenes) (8.85g, 25mmol) and THF (50ml), oil Bath heating maintain reflux state, drip rear back flow reaction 2 it is small when, be cooled to 0 degree with ice bath.By intermediate obtained above C28-b is dissolved in 100mlTHF, is added drop-wise in this solution, when reaction 3 is small after, filter, filter cake elutes with THF, and filtrate is spin-dried for, column layer Analyse (eluent：Dichloromethane/petroleum ether), obtain compound C28 1.9g, yield 41.0%.1H NMR(500MHz, Chloroform) δ 9.10 (d, J=3.1Hz, 1H), 8.71 (d, J=15.0Hz, 2H), 8.20-8.07 (m, 2H), 8.00 (d, J =15.0Hz, 1H), 7.88 (dd, J=21.7,9.1Hz, 3H), 7.77-7.53 (m, 5H), 7.45 (dd, J=15.0,2.9Hz, 1H), 7.40-7.29 (m, 2H), 7.25-7.12 (m, 6H), 7.08 (dd, J=15.0,3.0Hz, 1H), 7.01-6.85 (m, 2H),1.69(s,6H).
The synthesis of synthetic example 20.C30 compounds：
Nitrogen protection under, by intermediate M4 (4.90g, 10mmol),Phenoxazine(1.8g, 10mmol), Pd2(DBA)3 (0.06g, 0.1mmol), sodium tert-butoxide (2.4g, 25mmol), tri-butyl phosphine (0.06,0.2mmol), toluene (80mL), so When stirring reaction 4 is small under reflux afterwards.After the completion of reaction, enter water quenching go out ethyl acetate extraction, organic phase concentration, then use toluene Ethanol (1:1) recrystallize, compound C30-a (5.0g, 84.5%) is obtained after drying.
Under nitrogen protection, by C30-a (5.0g, 8.45mmol), N- (9,9- dimethyl -9H- fluorenes -2- bases) phenanthrene -9- amine (3.8g, 10mmol), Pd2(DBA)3(0.06g, 0.1mmol), sodium tert-butoxide (2.4g, 25mmol), tri-butyl phosphine (0.06, 0.2mmol), toluene (80mL), when then stirring reaction 4 is small under reflux.After the completion of reaction, filter, filter after being cooled to room temperature Cake dissolved silica gel postcooling room temperature crystallization with refluxing xylene, and compound C30 (5.5g, 72.3%) is obtained after filtering.1H NMR (500MHz, Chloroform) δ 8.98 (dd, J=14.2,3.7Hz, 1H), 8.84 (dd, J=14.2,3.7Hz, 1H), 8.53 (d, J=2.9Hz, 1H), 8.17-7.96 (m, 4H), 7.94-7.82 (m, 4H), 7.80-7.55 (m, 7H), 7.54-7.41 (m, 2H), 7.40-7.19 (m, 4H), 7.19-6.88 (m, 9H), 6.48 (dd, J=15.0,3.1Hz, 1H), 1.69 (s, 6H)
The synthesis of synthetic example 21.C38 compounds：
The synthesis of C38 compounds is identical with synthetic example 20, difference be byPhenoxazine, N- (9,9- dimethyl -9H- Fluorenes -2- bases) phenanthrene -9- amine is substituted for equivalent N- phenyl dibenzofurans -3- amine, N- phenyl-2-naphthylamines, obtain compound C38 (5.3g, 65.2%)1H NMR(500MHz,Chloroform)δ8.08–7.88(m,5H),7.75–7.66(m,1H),7.66– 7.58 (m, 2H), 7.59-7.51 (m, 3H), 7.51-7.17 (m, 14H), 7.15-6.94 (m, 8H), 6.48 (dd, J=15.0, 3.1Hz,1H).
Synthetic example 22
Synthesis without synthetic example C18, C34 compound is identical with synthetic example 5, and difference is 9,9'- spiral shells two [9H- fluorenes] -2- boric acid is substituted for the boric acid analog derivative of equivalent, 2- chlorine [9,10-d] thiazole phenanthrene is substituted for the chlorine of equivalent For heterocyclic derivative.
Synthetic example 23
Synthesis without synthetic example C19-C24, C26-C27, C55-C61 compound is identical with synthetic example 6, different It is the boric acid analog derivative that 2- dibenzothiophenes boric acid, (4- (diphenylamines) phenyl) boric acid are substituted for equivalent
Synthetic example 24
Synthesis and synthesis without synthetic example C29, C32, C33, C37, C45, C46, C50-C54, C62-C64 compound Embodiment 7 is identical, difference be by7H- benzos [C] carbazoleBe substituted for the secondary amine analog derivative of equivalent, by N- phenyl carbazoles- 3- boric acid is substituted for the boric acid analog derivative of equivalent.
Synthetic example 25.
Synthesis without synthetic example C31, C35, C36, C39-C44, C47 compound is identical with synthetic example 20, no Be byPhenoxazine, N- (9,9- dimethyl -9H- fluorenes -2- bases) phenanthrene -9- amine be substituted for the secondary amine analog derivative of equivalent
Device application examples
The structure of organic electroluminescence device is in comparative example of the present invention：ITO/2-TNATA(10nm)/NPB(80nm)/ EML(30nm)/ETL1(30nm)/LiF(1nm)/Al.Hole-injecting material uses 2-TNATA；Hole mobile material uses three virtues Amine material NPB；Emitting layer material uses red phosphorus photoinitiator dye (piq) 2Ir (acac), collocation feux rouges main body CBP；Electron transfer layer Select the electron transport material ETL1 of commercialization.Each functional layer material molecular structure is as follows：
The compound of the present invention of device embodiments 1. is as electron transport material
The glass plate for being coated with ITO (150nm) transparency conducting layer is ultrasonically treated in commercial detergent, in deionized water Middle flushing, in acetone: ultrasonic oil removing in alcohol mixed solvent (volume ratio 1: 1), is baked under clean environment and removes water completely Part, with ultraviolet light and ozone clean, and with the low energy cation beam bombarded surface of Satella (ULVAC)；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10-5~9 × 10-3Pa is evacuated to, upper Vacuum evaporation compound 2-TNATA on anode tunic is stated, forms the hole injection layer that thickness is 60nm；On hole injection layer Vacuum evaporation compound N PB, forms the hole transmission layer that thickness is 20nm, evaporation rate 0.1nm/s；
Electroluminescence layer is formed on above-mentioned hole transmission layer, concrete operations are:Using as the CBP of luminous layer main body [4, Bis- carbazoles of 4'-N, N'--biphenyl] it is placed in the cell of vacuum phase deposition equipment, using as (piq) 2Ir of dopant (acac) [two-(1- phenyl isoquinolin quinolines base) acetylacetone,2,4-pentanedione iridium (III)] is placed in another room of vacuum phase deposition equipment, with Different speed evaporates two kinds of materials at the same time, and the concentration of (piq) 2Ir (acac) is 5%, and evaporation total film thickness is 30nm；
Vacuum evaporation the compounds of this invention C1 forms the electron transfer layer that thick film is 20nm on luminescent layer, and speed is deposited in it Rate is 0.1nm/s；
The LiF of vacuum evaporation 0.5nm is as the Al layer conducts that electron injecting layer and thickness are 150nm on the electron transport layer The cathode of device.
2. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C7.
3. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C11.
4. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C14.
5. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C17.
6. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C18.
7. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C21.
8. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C23.
9. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C28.
10. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C46.
11. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C59.
12. the compounds of this invention of device embodiments is as electron transport material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced It is changed to compound C60.
13. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound C1 is replaced Compound ETL1 is changed to, material of main part CBP is replaced with into the compounds of this invention C3.
14. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C19.
15. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C22.
16. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C31.
17. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C33.
18. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C34.
19. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C51.
20. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C52.
21. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C55.
22. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C61.
23. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C63.
24. the compounds of this invention of device embodiments is as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound C64.
Device embodiments 25. choose the compounds of this invention and are used as while are used as electron transport material and phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by electric transmission Material ETL1 replaces with the compounds of this invention C11, and compound C3 is replaced with the compounds of this invention C22.
Device embodiments 26. choose the compounds of this invention and are used as while are used as electron transport material and phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by electric transmission Material ETL1 replaces with the compounds of this invention C14, and compound C3 is replaced with the compounds of this invention C34.
Device embodiments 27. choose the compounds of this invention and are used as while are used as electron transport material and phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by electric transmission Material ETL1 replaces with the compounds of this invention C59, and compound C3 is replaced with the compounds of this invention C55.
Device embodiments 28. choose the compounds of this invention and are used as while are used as electron transport material and phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by electric transmission Material ETL1 replaces with the compounds of this invention 60, and compound C3 is replaced with the compounds of this invention C61.
Comparative device embodiment 1. uses CBP to be used as electron transport material using ETL1 as phosphorescent light body material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Replace with compound CBP.
Comparative device embodiment 2. uses CBP using ETL1 as electron transport material, and to increase as phosphorescent light body material Add one layer thin CBP (5nm) exciton blocking layer material
Organic electroluminescence device is prepared using the method identical with embodiment 13, difference is, by compound C3 Compound CBP is replaced with, and the CBP between luminescent layer and electron transfer layer after one layer of 5nm of evaporation is as exciton barrier-layer.
Under same brightness, voltage, the electric current for measuring the organic electroluminescence device being prepared in each application examples are close Degree and current efficiency, measurement result see the table below 2.
2 the compounds of this invention of table is used as the measurement result of electron transport layer materials device
3 the compounds of this invention of table is used as the measurement result of phosphorescent light body material device
4 the compounds of this invention of table is used as the measurement result of electron transport material and phosphorescent light body material device at the same time
From the point of view of the experimental data of table 2, compared with comparative device embodiment 1, new organic materials of the invention are used for Electron transport material in organic electroluminescence device, the ETL1 that compares can effectively reduce landing voltage, improve electric current effect Rate, is electron transport material of good performance.This has higher triplet related with material of the present invention, due to ETL1's Triplet only has 1.8eV, when ETL1 directly connects with luminescent layer, since the triplet of red dye exciton is higher (2.0eV), thus can occur to cause Exciton quenching from main body or exciton to ETL1 generation energy transmissions, cause luminous efficiency Reduce.To verify that this, as a result, in comparative device embodiment 2, when using one layer there is the material compared with high triplet energy level to make For exciton barrier-layer when, it can be seen that the luminous efficiency of device can be improved, and the compounds of this invention is due to higher three Line state energy level and high electronic transmission performance, can further reduce voltage and improve luminous efficiency, while thus may not be used It can be achieved with high luminous efficiency using exciton barrier-layer, this just plays the effect for reducing batch production technique complexity.
Device embodiments 13-24 and comparative device embodiment 1 are can be seen that from the data in table 3, in organic electroluminescent In the case that other materials is identical in device architecture, series compound of the present invention replaces CBP in comparative device Examples 1 and 2 to make For feux rouges material of main part.Since material has electron donating group and drawing electron group at the same time in itself so that material has good Double carriers transmission performance, can effectively widen exciton recombination region so that and being quenched between triplet excitons significantly reduces, Luminous efficiency can be effectively thus improved, device data is shown, can as luminescent layer material of main part using material of the present invention Reduce device operating voltages and higher current efficiency show the excellent carrier transport balance of material in the present invention with And level-density parameter.Should be noted when carried as a result of the electron transport material with relatively low triplet, efficiency Increasing degree degree is not too big.
Device embodiments 25-28 is can be seen that compared with comparative device embodiment 1 from the data in table 4, in organic electroluminescence At the same time using the electron transport material and good double current-carrying having in the present invention compared with high triplet energy level in emitting device structure The material of main part of sub- transmission performance, in the case that other materials is identical, highly significant reduces operating voltage and significantly carries The luminous efficiency of device is risen.Show the excellent carrier transport balance and level-density parameter of material in the present invention.
Obviously, the above embodiments are merely examples for clarifying the description, and the restriction not to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (10)

1. a kind of perimidine derivative, it is characterised in that there is the structure shown in below formula (C)：
Wherein, Ar1With Ar2Differ, it is independent of each other to be selected from halogen, substituted or unsubstituted C1~C30Alkyl, substitutes or does not take The C in generation3~C30Cycloalkyl, substituted or unsubstituted C2-C30Heterocyclylalkyl, substitution or unsubstituted C6~C30Arylamino or miscellaneous Arylamino, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C2~C30Heteroaryl；
L1、L2It is independent of each other to be selected from singly-bound, substitution or unsubstituted C6-C30Arylamino or heteroaryl amino, substitution or do not take The C in generation6-C30Aryl, substituted or unsubstituted C2-C30Heteroaryl.
2. perimidine derivative according to claim 1, it is characterised in that the heteroaryl or the heteroaryl Hetero atom in base amino is at least one hetero atom selected from B, N, O, S, P, P (=O), Si and Se.
3. perimidine derivative according to claim 1 or 2, it is characterised in that：
The C1~C30Alkyl be selected from C1-C10Alkyl；
The C3~C30Cycloalkyl be selected from C3-C6Cycloalkyl；
The C6~C30Arylamino or heteroaryl amino include ammonia diaryl base, two (miscellaneous) arylaminos, triaryl amino Or three (miscellaneous) arylamino；
The C2-C30Heterocyclylalkyl be selected from there is C3-C10A ring skeleton atom and comprising at least one described heteroatomic miscellaneous Cycloalkyl；
The C6~C30Aryl be selected from C6-C20Aryl；
The C2~C30Heteroaryl be selected from C2-C20Heteroaryl.
4. according to claim 1-3 any one of them perimidine derivatives, it is characterised in that
The C1-C30Alkyl include methyl, ethyl, n-propyl, isopropyl, normal-butyl, n-hexyl, n-octyl, isobutyl group or Tert-butyl group etc.；
The C3-C30Cycloalkyl include cyclopropyl, cyclobutyl, cyclopenta and/or cyclohexyl etc.；
The C6-C30Arylamino or heteroaryl amino include diphenylamino, phenyl napthyl amino, tri- phenylaminos of 4-, 3- tri- Phenylamino, 4- [N- phenyl-N- (dibenzofurans -3- bases)] phenyl aminos or 4- [N- phenyl-N- (dibenzothiophenes -3- bases)] Phenyl amino etc.；
The C2-C30Heterocyclylalkyl includes tetrahydrofuran, pyrrolidines and/or thiophane；
The C6-C30Aryl include phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and its derivative Thing, fluoranthene base, triphenylene, pyrenyl, base,Base and aphthacene base；
The C2-C30Heteroaryl include thiazole, benzothiazole, phenanthro- imidazoles, phenanthro- benzothiophene benzimidazole, oxazole, evil Diazole, triazole, pyridine, pyrimidine, triazine, evil boron heterocycle, quinoline, isoquinolin, quinoxaline, quinazoline, benzoxazoles, phenanthro- are disliked Azoles, phenanthro- thiazole, bipyridyl, phenanthridines, phenanthroline, imidazopyridine, imidazopyrimidine, phenoxazine, phenthazine, dimethyl dihydro Acridine, the miscellaneous benzene of 1,2,5,10- tetrahydrochysene dibenzo boron, the miscellaneous benzene of 10,10- dimethyl -5,10- tetrahydrochysene dibenzo boron, 4- biphenyl acyl group, Furyl, thienyl, pyrrole radicals, benzofuranyl, benzothienyl, isobenzofuran-base, indyl, dibenzofuran group, Dibenzothiophene, carbazyl and its derivative, benzodioxole group etc..
5. according to claim 1-4 any one of them perimidine derivatives, it is characterised in that the derivative choosing From structure shown in following C1-C64：
6. any perimidine derivatives of claim 1-5 are used to prepare answering for organic electroluminescence device With.
7. application according to claim 6, it is characterised in that the perimidine derivative is used as electric transmission Material and/or phosphorescent light body material.
8. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate Functional layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；It is special Sign is：
The electron transport material of the electron transfer layer includes any described embedding diaza of naphthalene of at least one claim 1-5 Benzene derivative material.
9. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate Functional layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；It is special Sign is：
The phosphorescent light body material of the organic luminous layer includes any described embedding diaza of naphthalene of at least one claim 1-5 Benzene derivative material.
10. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, You Jifa on the substrate Light functional layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；It is special Sign is：
The electron transport material of the electron transfer layer includes any described embedding diaza of naphthalene of at least one claim 1-5 Benzene derivative material；And
The phosphorescent light body material of the organic luminous layer includes any described embedding diaza of naphthalene of at least one claim 1-5 Benzene derivative material.
CN201610965924.4A 2016-10-31 2016-10-31 A kind of perimidine derivative and its application Pending CN108017645A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108017647A (en) * 2016-10-31 2018-05-11 北京鼎材科技有限公司 A kind of perimidine derivative and its application
CN110156988A (en) * 2019-04-23 2019-08-23 湘潭大学 A kind of phenanthro- imidazole radicals aerotex and its preparation method and application
CN110684021A (en) * 2018-07-05 2020-01-14 乐金显示有限公司 Benzoxazole derivative having heteroaryl group and organic electroluminescent device comprising the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108017647A (en) * 2016-10-31 2018-05-11 北京鼎材科技有限公司 A kind of perimidine derivative and its application
CN110684021A (en) * 2018-07-05 2020-01-14 乐金显示有限公司 Benzoxazole derivative having heteroaryl group and organic electroluminescent device comprising the same
CN110684021B (en) * 2018-07-05 2022-12-20 乐金显示有限公司 Benzoxazole derivative having heteroaryl group and organic electroluminescent device comprising the same
CN110156988A (en) * 2019-04-23 2019-08-23 湘潭大学 A kind of phenanthro- imidazole radicals aerotex and its preparation method and application
CN110156988B (en) * 2019-04-23 2021-04-30 湘潭大学 Phenanthroimidazolyl triazine polymer and preparation method and application thereof

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Application publication date: 20180511