CN108017648A - A kind of perimidine derivative and its application - Google Patents

A kind of perimidine derivative and its application Download PDF

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CN108017648A
CN108017648A CN201610967549.7A CN201610967549A CN108017648A CN 108017648 A CN108017648 A CN 108017648A CN 201610967549 A CN201610967549 A CN 201610967549A CN 108017648 A CN108017648 A CN 108017648A
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unsubstituted
derivative
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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.
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), it is with good hole transport performance, but in electronic transmission performance side Face is poor, causes carrier transport unbalanced.And material of main part (special open 2002-352957 publications) then phase is used as using TAZ Instead, it has electron transport ability well, but cavity transmission ability is poor, can not equally realize that the carrier of equilibrium passes It is defeated.Therefore material of the exploitation with relatively balanced electronics and hole transport performance, it will have to the efficiency of phosphorescent devices bright Aobvious lifting.
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 nitrogen-containing heterocycle compound and its derivative, and The application that said derivative is used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field is further provided, specifically, the derivative is having In electroluminescent display, it is used as light emitting host material and/or electron transport material.
In order to solve the above technical problems, perimidine derivative of the present invention, has below formula (P) institute The structure shown：
Wherein, Ar is selected from halogen, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C3-C30Cycloalkyl, takes Generation or unsubstituted C2-C30Heterocyclylalkyl, substitution or unsubstituted C6-C30Arylamino or heteroaryl amino, substitution or do not take The C in generation6-C30Aryl, substituted or unsubstituted C2-C30Heteroaryl；
L is selected from singly-bound, substitution or unsubstituted C6-C30Arylamino or heteroaryl amino, substituted or unsubstituted C6-C30 Aryl, 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 is selected from structure shown in following P1-P82：
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 nitrogenous ring structure, there is high triplet, and And the presence of carbonyl causes molecule to have higher electron affinity, 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 evenly distributed in entirely On skeleton, thus there is very excellent carrier transport (triplet of its precursor structure is about 2.75eV).And By selecting the group with specific electron property, it can significantly improve the HOMO energy levels and lumo energy of material, make it With different carrier transports, so as to fulfill different function layer uses, can realize respectively as electron transfer layer material The purpose of material and phosphorescent light body material (the HOMO energy levels of parent molecule and the Cloud Distribution figure ginseng of lumo energy molecular orbit See attached drawing 1-2).In addition different structure and the substituent of size can also play the molecular weight that adjusts material molecule and symmetrical Property, 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 OLED Phosphorescent light body material in device, due to material possessed balanced and high bipolarity carrier transmission performance in itself, energy The efficiency roll-off of device under high illumination is enough effectively reduced, and plays 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 1 intermediate M5 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%).
Intermediate M1 (37g, 201mmol) and o-iodonitrobenzene (49.8g, 201mmol), sodium tert-butoxide (36g, 374mmol), toluene 60mL, nitrogen protection, Pd2 (dba) 3 (0.17g), tri-butyl phosphine (11ml, 10% toluene solution), is opened Stirring is opened, is heated to 100 DEG C of reflux, reacts 12h, reaction solution washing, organic phase concentration, crosses silicagel column, eluent is Shi You Mi ﹕ The ﹕ 1 of ethyl acetate=50, concentrates eluent, obtains intermediate M2 (48g products, yield 78.6%).
The iodo- 5- bromo nitrobenzenes (51.6g, 157mmol) of intermediate M2 (48g, 157mmol), 2-, sodium tert-butoxide (2.9g, 300mmol), toluene 50mL, nitrogen protection, 0.17 gram of Pd2 (dba) 3, tri-butyl phosphine (11ml, 10% toluene solution), is opened Stirring, is heated to 100 DEG C of reflux, reacts 12h, reaction solution washing, organic phase concentration, crosses silicagel column, eluent is Shi You Mi ﹕ second The ﹕ 1 of acetoacetic ester=50, concentrates eluent, obtains intermediate M3 (66g, yield 83.2%).
Intermediate M3 (66g, 119mmol), ethanol (3000ml), iron powder (36g, 635mmol), hydrochloric acid (20ml), heating To back flow reaction 5h, point board monitoring, which is reacted, to be completed, filtering, elutes filter cake with ethyl acetate, filtrate, which is received, does, and obtains intermediate M4 (59g, yield 84.4%)
Intermediate M4 (59g, 132mmol), is dissolved in 100ml acetic acid, adds 10g copper powders, and stirring is cooled to no more than 10 DEG C, with 60ml acetic acids isoamyl nitrite (45g, 384mmol), slowly it is added drop-wise in system, is added dropwise and is stirred at room temperature, Reaction end is controlled in contact plate, after the completion of reaction, liquid separation, organic phase is washed one time with aqueous sodium carbonate, dry, mixes silica gel, is used Petroleum ether crosses pillar, obtains intermediate M5 (26g, yield 47.9%) 1H NMR (500MHz, Chloroform) δ 8.55 (dd, J =7.5,1.4Hz, 1H), 8.11 (dd, J=7.5,1.4Hz, 1H), 8.05 (d, J=1.4Hz, 1H), 8.00 (d, J=7.5Hz, 1H), 7.63 (d, J=7.5Hz, 1H), 7.44 (ddd, J=14.8,7.5,1.5Hz, 2H), 7.36 (td, J=7.4,1.5Hz, 1H), 7.29 (d, J=7.5Hz, 1H), 7.16 (td, J=7.5,1.4Hz, 1H), 7.08 (dd, J=7.5,1.4Hz, 1H) can See that structure is correct.
The synthesis of 2 compound P1 of synthetic example
By intermediate M5 (4.26g, 10mmol), 4- terphenyls boric acid (2.74g, 10mmol), Pd (PPh3) 4 (0.58g, 0.5mmol), K2CO3 (5.3g, 50mmol), toluene (60mL) and EtOH (20mL) and distilled water (20mL) mixing, Ran Hou When stirring reaction 2 is small at 120 DEG C.After the completion of reaction, distilled water washing reaction system, is then extracted with ethyl acetate, is had Machine layer, organic layer is dried with MgSO4, and removes solvent with rotary evaporator, is carried out post separation to the residue for removing solvent, is obtained It is faint yellow solid (4.65g, 83%) to compound P1.1H NMR (500MHz, Chloroform) δ 9.10 (d, J= 3.0Hz, 1H), 8.25-8.12 (m, 1H), 8.00 (d, J=15.0Hz, 1H), 7.87 (dd, J=15.0,3.1Hz, 1H), 7.80-7.58 (m, 4H), 7.56-7.34 (m, 5H), 7.29-7.12 (m, 10H), 7.08 (dd, J=15.0,3.0Hz, 1H), can See that structure is correct.
The synthesis of 3 compound P2 of synthetic example
With synthetic example 2, difference is 4- terphenyl boric acid replacing with equivalent corresponding the synthetic method of P2 Boronic acid compounds.
The synthesis of 4 compound P3 of synthetic example
Using the method prepare compound P3 identical with synthetic example 2, difference is to replace with 4- terphenyl boric acid Equivalent (- 2 base of 6- phenylnaphthalenes) boric acid, after the completion of reaction, isolated white solid 4.03g, yield 75%.1H NMR (500MHz, Chloroform) δ 9.16 (d, J=2.9Hz, 1H), 8.26-8.12 (m, 1H), 8.06-7.93 (m, 3H), 7.87 (dd, J=15.0,3.1Hz, 1H), 7.79-7.56 (m, 6H), 7.55-7.33 (m, 7H), 7.26-7.12 (m, 2H), 7.08 (dd, J=15.0,3.0Hz, 1H), it is seen that structure is correct.
The synthesis of 5 compound P4 of synthetic example
By intermediate M5 (18.4g, 0.1mol), 5- phenyl -5,6- dihydrophenazine (2.58g, 0.1mol), sodium tert-butoxide Two palladium (0.92g, 0.001mol) of (19.2g, 0.2mol), 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, organic layer is extracted with ethyl acetate and is evaporated under reduced pressure, and column is carried out to obtained distillation residue Separate (eluent：Dichloromethane/n-hexane), obtain compound P4 (4.24g, 72%).1H NMR(500MHz, Chloroform) δ 8.25-8.13 (m, 1H), 8.00 (t, J=4.7Hz, 2H), 7.63 (d, J=7.5Hz, 1H), 7.53-7.35 (m, 3H), 7.29-7.11 (m, 8H), 7.08 (dd, J=7.5,1.4Hz, 3H), 7.03-6.91 (m, 5H), 6.48 (dd, J= 7.4,1.5Hz, 1H), it is seen that structure is correct.
The synthesis of 6 compound P15-18 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P5-P18 For the corresponding boronic acid compounds of equivalent.
The synthesis of 7 compound P19 of synthetic example
Using the method prepare compound P19 identical with synthetic example 2, difference is to replace with 4- terphenyl boric acid Equivalent dibenzofurans -2- boric acid, after the completion of reaction, isolated white solid 4.1g, yield 82%.1H NMR (500MHz, Chloroform) δ 9.17 (d, J=2.9Hz, 1H), 8.29 (d, J=2.7Hz, 1H), 8.24-8.12 (m, 1H), 8.05-7.93 (m, 2H), 7.87 (dd, J=15.0,3.1Hz, 1H), 7.66 (ddd, J=18.1,15.0,5.4Hz, 4H), 7.54 (dd, J=14.7,3.4Hz, 1H), 7.49-7.26 (m, 4H), 7.25-7.12 (m, 2H), 7.08 (dd, J=15.0, 3.0Hz, 1H), it is seen that structure is correct.
The synthesis of 8 compound P20-P22 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P20-P22 For the corresponding boronic acid compounds of equivalent.
The synthesis of 9 compound P23 of synthetic example
Using the method prepare compound P23 identical with synthetic example 2, difference is to replace with 4- terphenyl boric acid Equivalent dibenzothiophenes -2- boric acid, after the completion of reaction, isolated white solid 4.2g, yield 82%.1H NMR (500MHz, Chloroform) δ 9.21 (d, J=1.4Hz, 1H), 8.55 (d, J=1.4Hz, 1H), 8.45 (dd, J=7.5, 1.4Hz, 1H), 8.26-8.15 (m, 1H), 8.12 (dd, J=7.5,1.4Hz, 1H), 7.99 (dd, J=7.5,5.1Hz, 2H), 7.87 (ddd, J=7.3,5.1,1.4Hz, 2H), 7.71 (d, J=7.5Hz, 1H), 7.63 (d, J=7.5Hz, 1H), 7.56 (td, J=7.4,1.5Hz, 1H), 7.49-7.36 (m, 2H), 7.31 (td, J=7.5,1.5Hz, 1H), 7.25-7.14 (m, 2H), 7.08 (dd, J=7.5,1.4Hz, 1H), it is seen that structure is correct.
The synthesis of 10 compound P24-P35 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P24-P35 For the corresponding boronic acid compounds of equivalent.
The synthesis of 11 compound P36 of synthetic example
By M4 (4.1g, 10mmol) add into 50mlTHF, be cooled to -78 DEG C, start be added dropwise butyl lithium (4.8ml, 12mmol), drip insulation reaction 1 it is small when after, be added dropwise 4- ([1,1'- xenyl] -3- bases) -2- chloro-quinazolines (3.2g, 10mmol), after dripping insulation 30min, it is gradually brought to room temperature reaction completely, adds water base ethyl acetate extraction, organic phase Concentration, post separation (eluent is carried out to obtained distillation residue：Dichloromethane/n-hexane), compound P36 4.7g are obtained, Yield 76%.1H NMR (500MHz, Chloroform) δ 9.56 (d, J=3.0Hz, 1H), 8.28-8.07 (m, 3H), 8.07- 7.33 (m, 17H), 7.27-7.12 (m, 2H), 7.08 (dd, J=15.0,3.0Hz, 1H), it is seen that structure is correct.
The synthesis of 12 compound P37-P38 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P37-P38 For the corresponding boronic acid compounds of equivalent.
The synthesis of 13 compound P39 of synthetic example
Using the method prepare compound P39 identical with synthetic example 2, difference is to replace with 4- terphenyl boric acid Equivalent [4- (2- phenyl -1H- benzimidazole -1- bases) phenyl] boric acid, after the completion of reaction, isolated white solid 4.7g, Yield is 78%.1H NMR (500MHz, Chloroform) δ 9.11 (d, J=1.4Hz, 1H), 8.56 (dd, J=7.5, 1.6Hz, 1H), 8.38-8.23 (m, 2H), 8.23-8.13 (m, 1H), 8.00 (d, J=7.5Hz, 1H), 7.86 (dt, J= 12.0,6.0Hz, 1H), 7.83-7.74 (m, 5H), 7.71 (d, J=7.5Hz, 1H), 7.63 (d, J=7.5Hz, 1H), 7.58- 7.35 (m, 6H), 7.28 (td, J=7.5,1.4Hz, 1H), 7.23-7.13 (m, 2H), 7.08 (dd, J=7.5,1.4Hz, 1H).
The synthesis of 14 compound P40 of synthetic example
Using the method prepare compound P40 identical with synthetic example 11, difference be by 4- ([1,1'- xenyl]- 3- yls) -2- chloro-quinazolines replace with equivalent 2- chlorine phenanthro- [9,10-d] thiazole, after the completion of reaction, isolated white solid 4.2g, yield 74%.1H NMR (500MHz, Chloroform) δ 9.48 (d, J=2.9Hz, 1H), 8.98 (dd, J= 14.2,3.7Hz, 2H), 8.26-8.05 (m, 3H), 8.00 (d, J=15.0Hz, 1H), 7.87 (dd, J=15.0,3.1Hz, 1H), 7.77-7.54 (m, 6H), 7.50-7.32 (m, 2H), 7.27-7.12 (m, 2H), 7.08 (dd, J=15.0,3.0Hz, 1H), it is seen that structure is correct.
The synthesis of 15 compound P41 of synthetic example
Using the method prepare compound P41 identical with synthetic example 11, difference be by 4- ([1,1'- xenyl]- 3- yls) -2- chloro-quinazolines replace with chloro- 4, the 6- diphenylpyrimidins of equivalent 2-, after the completion of reaction, isolated white solid 4.0g, yield 72%.1H NMR (500MHz, Chloroform) δ 9.48 (d, J=2.9Hz, 1H), 8.29-8.13 (m, 2H), 8.04-7.82 (m, 6H), 7.77-7.32 (m, 10H), 7.27-7.13 (m, 2H), 7.08 (dd, J=15.0,3.0Hz, 1H), it is seen that structure is correct.The synthesis of 16 compound P42-P46 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P42-P46 For the corresponding boronic acid compounds of equivalent.
The synthesis of 17 compound P47 of synthetic example
Using the method prepare compound P47 identical with synthetic example 4, difference is 5- phenyl -5,6- dihydro fens Piperazine replaces with equivalent 7H- dibenzo [c, g] carbazole, after the completion of reaction, isolated white solid 3.2g, and yield 54%. 1H NMR (500MHz, Chloroform) δ 9.76 (d, J=3.1Hz, 1H), 8.54 (dd, J=14.6,3.4Hz, 2H), 8.30- 8.09 (m, 1H), 7.99 (ddd, J=7.9,5.8,2.6Hz, 3H), 7.71-7.28 (m, 12H), 7.16 (qdd, J=17.9, 14.9,3.9Hz, 4H), it is seen that structure is correct.
The synthesis of 18 compound P48 of synthetic example
With synthetic example 2, difference is to replace with 4- terphenyl boric acid the synthetic method of embodiment compound P48 The corresponding boronic acid compounds of equivalent.
The synthesis of 19 compound P49 of synthetic example
With synthetic example 4, difference is to replace with 4- terphenyl boric acid the synthetic method of embodiment compound P49 The corresponding boronic acid compounds of equivalent.
The synthesis of 20 compound P50-P52 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P50-P52 For the corresponding boronic acid compounds of equivalent.
The synthesis of 21 compound P53 of synthetic example
Using the method prepare compound P53 identical with synthetic example 4, difference is 5- phenyl -5,6- dihydro fens Piperazine replaces with equivalent 4,4'- dimethyl diphenylamines, after the completion of reaction, isolated white solid 4.1g, and yield 78%.1H NMR (500MHz, Chloroform) δ 8.26-8.11 (m, 1H), 8.01 (dd, J=9.0,6.0Hz, 2H), 7.63 (d, J= 15.0Hz, 1H), 7.54-7.35 (m, 3H), 7.27-7.02 (m, 11H), 6.48 (dd, J=15.0,3.1Hz, 1H), 2.32 (s, 6H), it is seen that structure is correct.
The synthesis of 22 compound P54 of synthetic example
With synthetic example 4, difference is to replace with 4- terphenyl boric acid the synthetic method of embodiment compound P54 The corresponding boronic acid compounds of equivalent.
The synthesis of 23 compound P55 of synthetic example
Using the method prepare compound P55 identical with synthetic example 4, difference is 5- phenyl -5,6- dihydro fens Piperazine replaces with equivalent N- ([1,1'- xenyl] -4- bases) -2 naphthylamines, and after the completion of reaction, isolated white solid 4.8g, is received Rate is 74%.1H NMR (500MHz, Chloroform) δ 8.25-8.11 (m, 1H), 8.01 (dd, J=9.0,6.0Hz, 2H), 7.80-7.67 (m, 3H), 7.66-7.59 (m, 2H), 7.59-7.32 (m, 14H), 7.25-7.02 (m, 4H), 6.48 (dd, J= 15.0,3.1Hz, 1H), it is seen that structure is correct.
The synthesis of 24 compound P56-P57 of synthetic example
With synthetic example 4, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P56-P57 For the corresponding boronic acid compounds of equivalent.
The synthesis of 25 compound P58-P60 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P58-P60 For the corresponding boronic acid compounds of equivalent.
The synthesis of 26 compound P61-P64 of synthetic example
With synthetic example 4, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P61-P64 For the corresponding boronic acid compounds of equivalent.
The synthesis of 27 compound P65 of synthetic example
With synthetic example 2, difference is to replace with 4- terphenyl boric acid the synthetic method of embodiment compound P65 The corresponding boronic acid compounds of equivalent.
The synthesis of 28 compound P66-P69 of synthetic example
With synthetic example 4, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P66-P69 For the corresponding boronic acid compounds of equivalent.
The synthesis of 29 compound P71-P76 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P71-P76 For the corresponding boronic acid compounds of equivalent.
The synthesis of 30 compound P77-P79 of synthetic example
With synthetic example 4, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P77-P79 For the corresponding boronic acid compounds of equivalent.
The synthesis of 31 compound P80-P81 of synthetic example
With synthetic example 2, difference is to replace 4- terphenyls boric acid the synthetic method of embodiment compound P80-P81 For the corresponding boronic acid compounds of equivalent.
The synthesis of 32 compound P82 of synthetic example
Under nitrogen protection, intermediate M5 (4.94g, 12mmol), isopropanol pinacol borate (3.0g, 13.2mmol) Mixed with THF (100ml), liquid nitrogen is down to -78 DEG C, and n-BuLi (5.3ml, 13.2mmol) is added dropwise, and it is small that 1.5 are kept the temperature after adding When.Add 100ml saturated aqueous ammonium chlorides and reaction, liquid separation is quenched, organic phase is spin-dried for after being dried with anhydrous sodium sulfate.Use oil Ether crystallizes, and obtains intermediate M6 4.5g, dries stand-by, yield 82.3%.
Under nitrogen protection, zinc powder (1.63g, 25mmol) and THF (30ml) are mixed, 2 drop 1,2- Bromofumes is added, draws After hair, start that 2- bromo- N- (2- bromophenyls)-N- aniline (10.07g, 25mmol) and the mixture of THF (50ml), oil bath is added dropwise Heating maintain reflux state, drip rear back flow reaction 2 it is small when, be cooled to 0 degree with ice bath.Intermediate M6 obtained above is molten In 100mlTHF, be 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 chromatography (elution Liquid：Dichloromethane/petroleum ether), obtain compound P82 2.03g, yield 35.4%.1H NMR(500MHz,Chloroform)δ 8.23-8.13 (m, 1H), 8.00 (t, J=4.7Hz, 2H), 7.63 (d, J=7.5Hz, 1H), 7.52-7.34 (m, 3H), 7.30- 7.04 (m, 11H), 7.03-6.88 (m, 5H), 6.48 (dd, J=7.4,1.5Hz, 1H), it is seen that structure is correct.
Device application examples
Compare the performance of these materials for convenience, the present invention devises a simple electroluminescence device, and device of the present invention should The concrete structure of organic electroluminescence device is in use-case：
ITO/2-TNATA(10nm)/NPB(80nm)/EML(30nm)/ETL1(30nm)/LiF(1nm)/Al。
Hole-injecting material uses 2-TNATA；Hole mobile material uses tri-arylamine group material NPB；Emitting layer material makes With red phosphorus photoinitiator dye (piq) 2Ir (acac), collocation feux rouges main body CBP；Electron transfer layer selects the electron transport material of commercialization ETL1.Each functional layer uses the structural formula of material as follows：
Substrate can use the substrate in conventional organic luminescence device, such as：Glass or plastics.In the Organic Electricity of the present invention Electroluminescence device selects glass substrate in making, and ITO makees anode material.
Hole transmission layer can use various tri-arylamine group materials, the institute in the organic electroluminescence device of the present invention makes The hole mobile material of selection is NPB.
Cathode can use metal and its mixture structure, such as Mg：Ag、Ca：Ag etc. or electron injecting layer/gold Belong to Rotating fields, such as LiF/Al, Li2O/Al common cathode structure.It is selected in the organic electroluminescence device of the present invention makes Cathode material is LiF/Al.
Compound P1-P82 in the application example respectively as the electron transport material in organic electroluminescence device and/or Emitting layer material, is prepared for multiple organic electroluminescence devices altogether, its structure is：ITO/2-TNATA(10nm)/NPB(80nm)/ EML(30nm)/ETL1(30nm)/LiF(1nm)/Al。
Organic electroluminescence device preparation process is as follows in the present embodiment：
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, is baked under clean environment and removes water completely in alcohol mixed solvent (volume ratio 1: 1) 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, is evacuated to 1 × 10-5-9×10-3Pa, above-mentioned Vacuum evaporation compound 2-TNATA on anode tunic, forms the hole injection layer that thickness is 60nm；It is true on hole injection layer Sky 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：This hair of luminescent layer material of main part will be used as Bright compound P1-P82 (with the organic luminous layer control materials of CBP [bis- carbazoles of 4,4'-N, N'--biphenyl] as device) is placed In the cell of vacuum phase deposition equipment, using as (piq) 2Ir (acac) of dopant [two-(1- phenyl isoquinolin quinolines base) second Acyl acetone iridium (III)] it is placed in another room of vacuum phase deposition equipment, two kinds of materials are evaporated with different speed at the same time, (piq) concentration of 2Ir (acac) is 5%, and evaporation total film thickness is 30nm；
Vacuum evaporation difference the compounds of this invention P1-P82 forms the electron transfer layer that thick film is 20nm on luminescent layer, And the electron transfer layer using Bphen as device is control, its evaporation rate is 0.1nm/s；
Vacuum evaporation thickness is the LiF of 0.5nm as electron injecting layer, thickness 150nm on electron transfer layer (ETL) Cathode of the Al layers as device.
Comparative device example 1
Using CBP as phosphorescent light body material, electron transport material is used as using ETL1.
Comparative device example 2
Using CBP as phosphorescent light body material, using ETL1 as electron transport material, and increase by one layer thin CBP (5nm) Exciton blocking layer material.
Under same brightness, the voltage and current effect for the organic electroluminescence device being prepared in each application examples is measured Rate, measurement result see the table below 1.
1 the compounds of this invention of table is used as the measurement result of electron transfer layer and/or light emitting host material devices
From the point of view of the experimental data of table 1, 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.
And device embodiments 22-42 and comparative device embodiment 1, the other materials phase in organic electroluminescence device structure With in the case of, series compound of the present invention is instead of CBP in comparative device Examples 1 and 2 as feux rouges material of main part.Due to material 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 being quenched between triplet excitons significantly reduces, thus can effectively improve hair Light efficiency, device data show, using material of the present invention as luminescent layer material of main part can reduce device operating voltages and compared with High current efficiency shows the excellent carrier transport balance and level-density parameter of material in the present invention.It should be noted Be due to employ the electron transport material with relatively low triplet, the lifting amplitude of efficiency is not too big.
Device embodiments 43-48 is used at the same time compared with comparative device embodiment 1 in organic electroluminescence device structure Have in the present invention compared with the electron transport material of high triplet energy level and the material of main part of good double carriers transmission performance, its In the case of his material identical, the luminous efficiency for reducing operating voltage and being obviously improved device of highly significant.Display 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 (P)：
Wherein, Ar is selected from halogen, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C3-C30Cycloalkyl, substitution or Unsubstituted C2-C30Heterocyclylalkyl, substitution or unsubstituted C6-C30Arylamino or heteroaryl amino, it is substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C2-C30Heteroaryl；
L is selected from singly-bound, substitution or unsubstituted C6-C30Arylamino or heteroaryl amino, substituted or unsubstituted C6-C30Virtue Base, 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 substituted or unsubstituted C1-C30Alkyl is selected from C1-C10Alkyl；
The substituted or unsubstituted C3-C30Cycloalkyl is selected from C3-C6Cycloalkyl；
The substituted or unsubstituted arylamino or heteroaryl amino include ammonia diaryl base, two (miscellaneous) arylaminos, three virtues Base amino or three (miscellaneous) arylaminos；
The substituted or unsubstituted C2-C30Heterocyclylalkyl, which is selected from, has C3-C10A ring skeleton atom and include at least one institute State heteroatomic Heterocyclylalkyl；
The substituted or unsubstituted C6-C30Aryl is selected from C6-C20Aryl；
The substituted or unsubstituted C2-C30Heteroaryl is 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 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-, 3- tri- Phenylamino, 4- [N- phenyl-N- (dibenzofurans -3- bases)] phenyl aminos or 4- [N- phenyl-N- (dibenzothiophenes -3- bases)] 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 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.
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 P1-P82：
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.
CN201610967549.7A 2016-10-31 2016-10-31 A kind of perimidine derivative and its application Pending CN108017648A (en)

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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
CN108017644A (en) * 2016-10-31 2018-05-11 北京鼎材科技有限公司 A kind of nitogen-contained heterocycle derivant and its application
CN108017646A (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
CN108336246A (en) * 2018-02-13 2018-07-27 长春海谱润斯科技有限公司 A kind of organic luminescent device

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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
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CN108336246A (en) * 2018-02-13 2018-07-27 长春海谱润斯科技有限公司 A kind of organic luminescent device
CN108336246B (en) * 2018-02-13 2019-07-26 长春海谱润斯科技有限公司 A kind of organic luminescent device

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Application publication date: 20180511