CN105461611A - Spirofluorene benzyl fluorescent material - Google Patents

Spirofluorene benzyl fluorescent material Download PDF

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CN105461611A
CN105461611A CN201510991946.3A CN201510991946A CN105461611A CN 105461611 A CN105461611 A CN 105461611A CN 201510991946 A CN201510991946 A CN 201510991946A CN 105461611 A CN105461611 A CN 105461611A
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replacement
phenyl
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base
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曹建华
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Abstract

The invention discloses a luminescent material with a spirofluorene benzyl unit. 9,9'-spirobifluorene molecules are taken as a main body to prepare a series of luminescent materials (see general formula I) by connection with different substituent groups. The compound provided by the invention has the characteristics of high glass transition temperature, high triplet state energy level, high quantum efficiency and the like, and can be applied to organic electroluminescent LEDs to serve as a luminescent material. Moreover, raw materials are easily available, the preparation is simple and convenient, the overall yield is high, and the cost of the luminescent material is greatly reduced.

Description

Spiral shell fluorenes benzyl fluorescent material
Technical field
The invention belongs to ORGANIC ELECTROLUMINESCENCE DISPLAYS field, relate to a series of spiral shell fluorenes benzyl fluorescent material.
Background technology
First organic electroluminescent (being called for short OLED) and relevant research have found the electro optical phenomenon of organic compound single-crystal anthracene as far back as people such as pope in 1963.A kind of amorphous membranous type device has been made by the method for evaporation organic molecule by the Kodak of the U.S. in 1987, has been dropped within 20V by driving voltage.This kind of device owing to having ultra-thin, all solidstate, luminous, brightness is high, visual angle is wide, fast response time, driving voltage is low, power consumption is little, bright in luster, contrast gradient is high, technological process is simple, good temp characteristic, can realize the advantages such as soft display, flat-panel monitor and area source can be widely used in, therefore obtain and study widely, develop and use.
Electroluminescent organic material is divided into two large classes: organic electroluminescent fluorescent materials and organic electromechanical phosphorescent material, wherein organic electroluminescence fluorescence is the result of singlet excitons Radiation-induced deactivation, different from photoluminescence, in Organic Light Emitting Diodes, triplet excitons and singlet exciton generate simultaneously.The generation ratio of usual singlet exciton and triplet excitons is 1:3, and prohibit effect according to the taboo meter of quantum statistics, mainly there is non-radiative decay in triplet excitons, minimum to luminescence contribution, only has singlet exciton radioluminescence, therefore, concerning organic/electrostrictive polymer fluorescent device, the basic reason that luminous efficiency is difficult to improve is that luminescence process is the luminescence of singlet exciton.
Organic luminescent device research early stage, namely people propose the imagination of triplet emission, Forrest group octaethylporphyrin platinum dopant has made red electrophosphorescence luminescent device in small molecule host material 8-hydroxyquinoline aluminum, external quantum efficiency reaches 4%, so far, the research of electroluminescent phosphorescence starts to obtain academia and pays close attention to greatly, and organic electrophosphorescenpolymer research obtains and develops rapidly in several years subsequently.Wherein complex of iridium because of its triplet lifetime shorter, there is good luminescent properties, develop at most also be the best a kind of phosphor material of application prospect, because phosphor material has stronger triplet state quencher in solids, general is all as doping guest materials with complex of iridium, doped body material is made, by energy trasfer or be directly trapped in by exciton and luminously on object obtain high-luminous-efficiency with the material of wider band gap.
Organic electroluminescence green phosphorescent material studies the earliest, is also develop a most ripe class material.Hino in 2004 etc. have made phosphorescent devices by the mode of spin coating, and external quantum efficiency is 29cd/A to the maximum, and the high-level efficiency that this simple Devices structure realizes is attributable to the good film-forming properties of material and the main body energy trasfer to guest materials.Adachi etc. are by (ppy) 2ir (acac) is doped in TAZ, and using HMTPD as hole transmission layer, obtaining maximum external quantum efficiency is 20%, energy efficiency is the green device of 65lm/W, as calculated, its internal quantum efficiency is almost close to 100%, and triplet excitons and singlet exciton are utilized simultaneously.
Summary of the invention
The object of this invention is to provide a kind of spiral shell fluorenes benzyl fluorescent material.
Spiral shell fluorenes benzyl fluorescent material provided by the invention, its general structure is such as formula shown in I:
In described formula I, R 1, R 2all alone be selected from following group any one:
and hydrogen atom, and R 1and R 2be asynchronously hydrogen;
R 5be selected from the straight chain containing C1-C20 or aliphatic group, the aromatic base of C5-C60, the polycyclic aromatic base of C5-C60 with side chain;
R 3, R 4all independently selected from that replace or unsubstituted C 6-C 60aryl, replacement or unsubstituted C 6-C 60aryloxy, replacement or unsubstituted C 6-C 60arylthio, replacement or unsubstituted C 6-C 60virtue phosphino-, replacement or unsubstituted C 6-C 60virtue silica-based, replace or unsubstituted C 6-C 60virtue boryl, replacement or unsubstituted C 2-C 60any one in heterocyclic aryl;
And R 3and R 4can be connected to form represent and replace position;
The C of described replacement 6-C 60the C of aryl, replacement 6-C 60the C of aryloxy, replacement 6-C 60the C of arylthio, replacement 6-C 60the C of virtue phosphino-, replacement 6-C 60virtue is silica-based, the C of replacement 6-C 60the C of virtue boryl, replacement 2-C 60in heterocyclic aryl, substituting group be selected from methyl, ethyl, the tertiary butyl, methoxyl group, cyano group, phenoxy group, halogen atom and containing 2 ~ 8 carbon atoms aliphatic group in any one;
Described replacement or unsubstituted C 2-C 60in heterocyclic aryl, at least one contains the ring texture of at least one in N, O and S atom.
Concrete, described C 6-C 60aryl be selected from phenyl, naphthyl, xenyl, anthryl, dianthranide base, to tert-butyl-phenyl, 2,4-difluorophenyl, 4-(N, N-dimethyl amido) phenyl, 4-(N, N-phenylbenzene amido) phenyl, any one in 3-(N, N-phenylbenzene amido) phenyl, pyrenyl, naphthacenyl, phenanthryl, benzo phenanthryl, benzo anthryl, benzo pyrenyl and fluorenyl;
Described C 6-C 60aryloxy be selected from 4-Phenoxyphenyl, dibenzo [b, d] furans-2-base, dibenzo [b, d] furans-4-base, cumarone-2-base, cumarone-5-base and cumarone-7-base any one;
Described C 6-C 60arylthio be selected from dibenzo [b, d] thiophene-2-base, dibenzo [b, d] thiophene-4-base, 4-benzene sulfoxide group phenyl, 4-benzene sulfuryl phenyl, thionaphthene-2-base, thionaphthene-5-base and thionaphthene-7-base any one;
Described C 6-C 60virtue phosphino-be selected from 4-(two phenenyl phosphinyl) phenyl, 3-(two phenenyl phosphinyl) phenyl and dibenzo [b] phosphine oxide-5-(4-phenyl)-4-base any one;
Described C 6-C 60virtue is silica-based be selected from 4-(triphenyl is silica-based) phenyl, 4-(diphenyl methyl is silica-based) phenyl, 3-(triphenyl is silica-based) phenyl and 3-(diphenyl methyl is silica-based) phenyl any one;
Described C 6-C 60virtue boryl be selected from 4-(two (2,4,6-trimethylammonium) phenyl)-borine phenyl, dibenzo [b, d] borine-5-phenyl-4-base and triphenyl boryl any one;
Described C 2-C 60heterocyclic aryl be selected from as shown in the formula any one in group shown in II-1 to formula II-15:
In described formula II-1 ~ II-15, Z 1, Z 2, Z 3independently be selected from hydrogen, deuterium hydrogen, halogen atom, hydroxyl, itrile group, nitro, amino, amidino groups, diazanyl, hydrazone group, carboxyl or its carboxylate salt, sulfonic group or its sulfonate, phosphate or its phosphoric acid salt, C 1-C 60alkyl, C 2-C 60thiazolinyl, C 2-C 60alkynyl, C 1-C 60alkoxyl group, C 3-C 60cycloalkyl group, C 3-C 60cycloalkenyl group, C 6-C 60aryl, containing C 1-C 10the C of alkyl 6-C 60aryl, replacement or unsubstituted C 6-C 60aryloxy, replacement or unsubstituted C 6-C 60arylthio, replacement or unsubstituted C 2-C 60any one in heterocyclic aryl;
The C of described replacement 6-C 60the C of aryloxy, replacement 6-C 60the C of arylthio and replacement 2-C 60in heterocyclic aryl, substituting group be selected from methyl, ethyl, the tertiary butyl, methoxyl group, cyano group, phenoxy group, halogen atom or containing 2 ~ 8 carbon atoms aliphatic group in any one;
X 1it is the integer of 1 ~ 4;
X 2it is the integer of 1 ~ 3;
X 3it is the integer of 1 ~ 2;
X 4it is the integer of 1 ~ 6;
X 5it is the integer of 1 ~ 5;
T 1for oxygen or sulphur atom.
More specifically, R in above-mentioned formula I 5definition in, the straight chain of C1-C20 or at least one be specifically selected from the aliphatic group of side chain in the alkyl of the alkyl of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C2-C6, the alkyl of C2-C18, the alkyl of C3-C14, the alkyl of C4-C15, the alkyl of C5-C10, the alkyl of C6-C8, the alkyl of C7-C15 and C8-C15; Wherein, described alkyl specifically can be alkyl, cycloalkyl or thiazolinyl;
More specifically, compound shown in described formula I is for as shown in the formula any one in compound shown in I001 to formula I080:
In addition; compound shown in Organic Light Emitting Diode material containing compound shown in the formula I that the invention described above provides and this formula I shown in the application prepared in Organic Light Emitting Diode material and this formula I compound as emitting layer material in the application prepared in organic electroluminescence device with using compound shown in formula I as the organic electroluminescence device of luminescent layer, also belong to protection scope of the present invention.Described organic electroluminescence device is specially organic electroluminescence fluorescence radiation device; Described Organic Light Emitting Diode material is specially organic fluorescence diode material.The fluorescence emission wavelengths of described organic electroluminescence fluorescence radiation device is specially 380-440nm, is specially 382,388,416 or 438nm.
Concrete, described organic electroluminescence device is made up of transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively.
Wherein, the material forming described transparent substrate is glass or flexible substrate;
The material forming described anode layer is inorganic materials or organic conductive polymer; Wherein, described inorganic materials is tin indium oxide, zinc oxide, zinc tin oxide, gold and silver or copper; Described organic conductive polymer is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material forming described hole injection layer is TDATA, m-MTDATA or 2-TNATA:
The structural formula of described TDATA is as follows:
The structural formula of described m-MTDATA is as follows:
The structural formula of described 2-TNATA is as follows:
The material forming described hole transmission layer is NPB or TPD:
The structural formula of described NPB is as follows:
The structural formula of described TPD is as follows:
The material forming described organic luminous layer forms for compound shown in described formula I or by compound shown in described formula I and dopant material;
Wherein, described dopant material is compound shown in FIrpic, DMAC-DPS, BCz-DPS, PXZ-DPS, PTCz-DPS, BPT-DPS, DPVQ or DACQ;
The quality of compound shown in described formula I-and the mass ratio of described dopant material are 1-10:90;
Form the material of described electron transfer layer for compound shown in Liq, Alq3, Gaq3 or BAlq;
Wherein, the structural formula of compound shown in Liq is as follows:
The material forming described cathode layer is selected from any one or any alloys of two kinds of compositions in following element or the fluorochemical of following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
More specifically, the thickness of described hole injection layer is 30-50nm; Be specially 30nm;
The thickness of described hole transmission layer is 5-15nm; Be specially 10nm;
The thickness of described organic luminous layer is 10-100nm; Be specially 40nm;
The thickness of described electron transfer layer is 10-30nm; Be specially 50nm;
The thickness of described cathode layer is 90-110nm, is specially 60nm.
The present invention is based on electromechanical phosphorescent material and the good film forming properties of thermic delayed fluorescence material require and there is the material of main part that higher triplet etc. requires and arrange in pairs or groups, material of main part will have good carrier transport speed and thermostability simultaneously, to improve the performance of luminescent device, the present invention proposes a series of luminescent material with spiral shell fluorenes aminobenzyl unit, with 9, 9 '-spiral shell two fluorenes molecule is main body, process and different substituting groups connect has prepared a series of luminescent material (see general formula I), the compound that the present invention relates to has high second-order transition temperature, high triplet, the features such as high quantum yield, and raw material is easy to get, prepare easy, overall yield is high, the cost of the luminescent material greatly reduced.
Accompanying drawing explanation
Fig. 1 is the synthetic route of compound shown in formula I;
Fig. 2 is the luminous spectrogram that the embodiment of the present invention 1 prepares gained Formula I001.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
Compound shown in formula I provided by the invention can obtain according to the preparation of method shown in Fig. 1.In Fig. 1 in intermediate compound structural formula, R 1, R 2, R 3, R 4definition identical with the definition in formula I.
Following embodiment the testing tool of performance test is carried out to OLED material and device and method as follows:
Brightness and tristimulus coordinates: use spectrum scanner PhotoResearchPR-715 test;
Current density and a bright voltage: use digital sourcemeter Keithley2420 test;
Power efficiency: use NEWPORT1931-C test.
Below by way of specific embodiment, the invention will be further elaborated, but the present invention is not limited to this specific examples.
Employ following abbreviation in an embodiment:
The preparation of embodiment 1 Compound I 001
The first step: 2-bromo-4, the preparation of 4 '-dimethyl diphenyl (I-1)
4 of 36.5g (0.2mol), 4 '-dimethyl diphenyl is dissolved in 360ml anhydrous methylene chloride, 1 iodine is added under room temperature, stirring reaction 1 hour, the bromine being slowly added dropwise to 35.2g (0.22mol) is dissolved in the solution of methylene dichloride, and stirring reaction 24 hours adds the saturated aqueous solution of sodium bisulfite of 120ml, stirring reaction 1 hour, separate organic phase, organic phase anhydrous sodium sulfate drying, filter, filtrate reduced in volume is done, use silicagel column separation and purification, concentrating under reduced pressure is done, and obtains the I-1 of 48g, colorless oil, yield 92%.
Second step: the preparation of intermediate compound I-2
The 20g intermediate compound I-1 that upper step is obtained and the tetrahydrofuran (THF) stirring and dissolving of 400ml drying; under nitrogen protection;-78 DEG C are cooled to liquid nitrogen bath; be added dropwise to the 2.5M n-Butyl Lithium-hexane solution of 34ml; stirring reaction 1 hour; add 2, the 7-bis-bromo-9-Fluorenones of 31g, stirring reaction 1 hour in batches; be raised to room temperature; add the saturated aqueous ammonium chloride of 200ml, separate organic phase, aqueous phase is extracted with ethyl acetate; organic phase concentrating under reduced pressure is done; obtain the intermediate compound I-2 of 32.7g, brown oil, yield 82.5%.
3rd step: the preparation of intermediate compound I-3
The intermediate compound I-2 of 30g and the chloroform stirring and dissolving of 150ml, add the vitriol oil of 2ml, temperature rising reflux reacts 8 hours, cool to room temperature, wash three times with water, organic phase is dry, filters, filtrate reduced in volume is done, residue over silica gel column separating purification, then use recrystallizing methanol, obtain the intermediate compound I-3 of 22.6g, yellow solid, yield 78%.
4th step: the preparation of intermediate compound I-4
Under nitrogen protection, the K of the intermediate compound I-3 of 17.8g, the anhydrous sodium carbonate of 14.8g, the palladium of 0.9g and 13g 4[Fe (CN) 6] mixing, add the Virahol of DMF and 10ml of 200ml, be warming up to 130 DEG C of stirring reactions 5 hours, cool to room temperature, add 400ml water in reaction solution.With 100ml extraction into ethyl acetate three times.Organic phase merges, and with the water washing of 100ml saturated common salt, organic phase anhydrous sodium sulfate drying, filters, and filtrate reduced in volume is dry, residue over silica gel column separating purification, then uses ethyl alcohol recrystallization, obtains the intermediate compound I-4 of 12.8g, yellow solid, yield 92%.
5th step: the preparation of intermediate compound I-5
The tetracol phenixin mixing of the intermediate compound I-4 of 12g and NBS and 480ml of 12g, then add the radical initiator azo-bis-isobutyl cyanide of 50mg, be warming up to return stirring and react 12 hours, cool to room temperature, filter, filtrate water washes three times, organic phase anhydrous sodium sulfate drying, filter, filtrate reduced in volume is done, and residue over silica gel column separating purification, obtains the intermediate compound I-5 of 15.7g, yellow solid, yield 93%.
6th step: the preparation of Formula I001
The carbazole of 4g and the DMF stirring and dissolving of 80ml, ice-water bath is lowered the temperature, less than 10 DEG C sodium hydride (65% oil dispersion) stirring reactions in batches adding 1g 1 hour, then adds the intermediate compound I-5 of 6g, stirring reaction 12 hours, poured into by reaction solution in the frozen water of 240ml, filter, filter cake washes three times with water, recycle silicon glue column separating purification, obtain the intermediate compound I-5 of 5.2g, white solid, yield 66%.
Experimental data:
(1) 1HNMR(δ、CDCl 3)：5.35(4H,s)，6.52(2H,s)，6.95～7.02(4H,m)，7.15～7.25(8H,m)，7.34～7.39(4H,m)，7.57～7.60(2H,d)，7.69～7.73(2H,q)，7.91～7.93(2H,d)，8.05～8.08(4H,d)。Confirm that the material be obtained by reacting is Compound I 001 really;
(2) HRMS:C 53h 32n 4, standard molecular weight 724.26, test result 725.40 [M+H];
(3) second-order transition temperature (DSC): 147.8 DEG C;
(4) UV maximum absorption wavelength (DCM): 280nm;
(5) fluorescence emission wavelengths (DCM): 382nm (as shown in Figure 2).
The preparation of embodiment 2 Compound I 017
The first step: the preparation of intermediate compound I-4
Under nitrogen protection; intermediate compound I-3 prepared by the embodiment 1 of 10.4g be dissolved in 120ml drying tetrahydrofuran (THF), be placed in cryostat, and be cooled to-78 DEG C; be added dropwise to the 2.5M n-Butyl Lithium-hexane solution of 20ml; stirring reaction 30 minutes, the DEET being added dropwise to 9.2g is dissolved in the solution of tetrahydrofuran (THF); stirring reaction 30 minutes; rise to stirring at room temperature and react 1 hour, add the 3M diluted hydrochloric acid aqueous solution of 100ml, stirring reaction 1 hour.Be extracted with ethyl acetate three times.Organic phase merges, and with the water washing of 100ml saturated common salt, organic phase anhydrous sodium sulfate drying, filters, and filtrate reduced in volume is dry, residue over silica gel column separating purification, then uses ethyl alcohol recrystallization, obtains the intermediate compound I-4 of 10.0g, yellow solid, yield 88%.
Second step: the preparation of intermediate compound I-5
This step synthetic operation is with reference to the 5th step of embodiment 1, and the 5th step intermediate compound I-4 of intermediate compound I-4 alternative embodiment 1 prepared by step, silicagel column separation and purification, obtains yellow solid I-5, yield 90%.
3rd step: the preparation of Formula I017
This step synthetic operation is with reference to the 6th step of embodiment 1, and with the carbazole of pentanoic alternative embodiment 1 the 6th step, the intermediate compound I-5 of intermediate compound I-5 alternative embodiment 1 the 6th step prepared by step, silicagel column separation and purification, obtains the solid I017 of white, yield 72%.
Experimental data:
(1) 1HNMR(δ、CDCl 3)：3.96(4H,s)，6.52～6.58(6H,m)，7.02～7.09(18H,m)，7.16～7.23(14H,m)，7.34～7.39(4H,m)。Confirm that the material be obtained by reacting is Compound I 017 really;
(2) HRMS:C 65h 46n 2o 2, standard molecular weight 886.35, test result 909.42 [M+Na];
(3) second-order transition temperature (DSC): 134.5 DEG C;
(4) UV maximum absorption wavelength (DCM): 286nm;
(5) fluorescence emission wavelengths (DCM): 388nm.
The preparation of embodiment 3 Compound I 051
The first step: the preparation of intermediate compound I-4
Under nitrogen protection, the intermediate compound I-3 of embodiment 1 preparation of 10.0g is dissolved in the N of 120ml drying, in dinethylformamide, add the cuprous iodide of the thiophenol of 5.5g and the Carbon Dioxide caesium of 13.0g and 38mg, stirring reaction 30 minutes, add the N of 0.5ml again, N '-dimethyl quadrol, be warming up to 100 DEG C of stirring reactions 12 hours, cool to room temperature, reaction solution is poured in the diluted hydrochloric acid aqueous solution of 500ml, stirring reaction 1 hour, filter, filter cake washes with water, use dichloromethane-ethanol recrystallization again, obtain the intermediate of 9.3g, yellow solid, yield 84%.
The above-mentioned intermediate of 9.3g is dissolved in the metachloroperbenzoic acid (75%) in the methylene dichloride of 150ml, in batches adding 19g, stirring reaction 12 hours, filter, the aqueous sodium hydroxide solution of filtrate 0.5M washes three times, organic phase concentrating under reduced pressure is done, and uses toluene-ethano recrystallization, obtains the intermediate compound I-4 of 9.0g, white solid, yield 88%.
Second step: the preparation of intermediate compound I-5
This step synthetic operation is with reference to the 5th step of embodiment 1, and the 5th step intermediate compound I-4 of intermediate compound I-4 alternative embodiment 1 prepared by step, silicagel column separation and purification, obtains yellow solid I-5, yield 86%.
3rd step: the preparation of Formula I051
This step synthetic operation is with reference to the 6th step of embodiment 1, and with the carbazole of thiodiphenylamine alternative embodiment 1 the 6th step, the intermediate compound I-5 of intermediate compound I-5 alternative embodiment 1 the 6th step prepared by step, silicagel column separation and purification, obtains the solid I051 of white, yield 82%.
Experimental data:
(1) 1HNMR(δ、CDCl 3)：3.79(4H,s)，6.56～6.61(8H,m)，7.05～7.11(12H,m)，7.17～7.23(16H,m)，7.35～7.39(2H,m)。Confirm that the material be obtained by reacting is Compound I 051 really;
(2) HRMS:C 63h 42n 2o 4s 4, standard molecular weight 1018.20, test result 1018.32 [M];
(3) second-order transition temperature (DSC): 178.3 DEG C;
(4) UV maximum absorption wavelength (DCM): 295nm;
(5) fluorescence emission wavelengths (DCM): 416nm.
The preparation of embodiment 4 Compound I 073
The first step: the preparation of intermediate compound I-4
Under nitrogen protection, the embodiment 1 of 10.0g prepare intermediate compound I-3, the dimethylbenzene adding 120ml drying, 10.0g sulphur dioxygen for thiodiphenylamine and the Anhydrous potassium carbonate of 8.2g and the cuprous iodide of 38mg, stirring reaction 30 minutes; add the Tetramethyl Ethylene Diamine of 0.5ml again; be warming up to return stirring and react 12 hours, cool to room temperature, filter; filter cake methylene dichloride is washed; filtrate is concentrated dry, and resistates crosses silicagel column separation and purification, obtains the intermediate compound I-4 of 13.5g; yellow solid, yield 84%.
Second step: the preparation of intermediate compound I-5
This step synthetic operation is with reference to the 5th step of embodiment 1, and the 5th step intermediate compound I-4 of intermediate compound I-4 alternative embodiment 1 prepared by step, silicagel column separation and purification, obtains yellow solid I-5, yield 65%.
3rd step: the preparation of Formula I073
This step synthetic operation is with reference to the 6th step of embodiment 1, and the intermediate compound I-5 of intermediate compound I-5 alternative embodiment 1 the 6th step prepared by step, silicagel column separation and purification, obtains the solid I073 of white, yield 83%.
Experimental data:
(1) 1HNMR(δ、CDCl 3)：5.38(4H,s)，6.52(2H,d)，6.58～6.62(12H,m)，7.12～7.20(22H,m)，7.33～7.38(4H,m)，7.92～7.94(2H,d)，8.05～8.08(2H,d)。Confirm that the material be obtained by reacting is Compound I 073 really;
(2) HRMS:C 75h 48n 4o 4s 2, standard molecular weight 1132.31, test result 1133.34 [M+H];
(3) second-order transition temperature (DSC):;
(4) UV maximum absorption wavelength (DCM): 276nm;
(5) fluorescence emission wavelengths (DCM): 438nm.
Here is the Application Example of the compounds of this invention:
Embodiment 5, fabricate devices OLED-1 ~ OLED-5
1) the glass substrate supersound process 30 minutes in clean-out system will ITO conductive layer being coated with, rinse in deionized water, in acetone/ethanol mixed solvent ultrasonic 30 minutes, be baked to complete drying under a clean environment, 10 minutes are irradiated with ultraviolet rays cleaning machine, and with low energy positively charged ion bundle bombarded surface.
2) the above-mentioned ito glass substrate handled well is placed in vacuum chamber, is evacuated to 1 × 10 -5~ 9 × 10 -4pa, on above-mentioned anode tunic, evaporation compound 2-TNATA is as hole injection layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
3) on above-mentioned hole injection layer, continuing evaporation NPB is hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 10nm;
4) on hole transmission layer, continue the evaporation embodiment of the present invention 1 gained Compound I 001 is dopant material as material of main part and DPVQ, Compound I 001 is 90:10 with the mass ratio of DPVQ, as the organic luminous layer of device, evaporation rate is 0.1nm/s, and the thickness of evaporation gained organic luminous layer is 40nm;
5) on organic luminous layer, continue the electron transfer layer of evaporation one deck Liq as device, evaporation rate is 0.1nm/s, and evaporation thickness is 50nm;
6) on electron transfer layer successively evaporation magnesium/ag alloy layer as the cathode layer of device, wherein the evaporation rate of magnesium/ag alloy layer is 2.0 ~ 3.0nm/s, evaporation thickness is 100nm, and the mass ratio of magnesium and silver is 1:9, obtains OLED OLED-1 provided by the invention.
According to upper identical step, by step 4) in Compound I 001 replace with embodiment 3 gained Compound I 051, obtain OLED-2 provided by the invention;
According to upper identical step, by step 4) in Compound I 001 replace with Compound I 053, obtain OLED-3 provided by the invention;
According to upper identical step, by step 4) in Compound I 001 replace with embodiment 2 gained Compound I 017, obtain OLED-4 provided by the invention;
According to upper identical step, by step 4) in Compound I 001 replace with embodiment 4 gained Compound I 073, obtain OLED-5 provided by the invention;
The performance test results of obtained device OLED-1 to OLED-5 is as shown in table 1.
The performance test results of table 1, OLED-1 to OLED-5
As from the foregoing, it is low that the device that shown in formula I provided by the invention, organic materials is prepared into plays bright voltage, and brightness remains on 500cd/m 2under condition, the 9cd/A that the power efficiency of device all exceedes, and also under device does not encapsulate intact condition, its transformation period all reaches 600 hours.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to above-described embodiment, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.

Claims (10)

1. compound shown in formula I,
In described formula I, R 1, R 2all alone be selected from following group any one:
and hydrogen atom, and R 1and R 2be asynchronously hydrogen;
R 5be selected from the straight chain containing C1-C20 or aliphatic group, the aromatic base of C5-C60, the polycyclic aromatic base of C5-C60 with side chain;
R 3, R 4all independently selected from that replace or unsubstituted C 6-C 60aryl, replacement or unsubstituted C 6-C 60aryloxy, replacement or unsubstituted C 6-C 60arylthio, replacement or unsubstituted C 6-C 60virtue phosphino-, replacement or unsubstituted C 6-C 60virtue silica-based, replace or unsubstituted C 6-C 60virtue boryl, replacement or unsubstituted C 2-C 60any one in heterocyclic aryl;
And R 3and R 4can be connected to form represent and replace position;
The C of described replacement 6-C 60the C of aryl, replacement 6-C 60the C of aryloxy, replacement 6-C 60the C of arylthio, replacement 6-C 60the C of virtue phosphino-, replacement 6-C 60virtue is silica-based, the C of replacement 6-C 60the C of virtue boryl, replacement 2-C 60in heterocyclic aryl, substituting group be selected from methyl, ethyl, the tertiary butyl, methoxyl group, cyano group, phenoxy group, halogen atom and containing 2 ~ 8 carbon atoms aliphatic group in any one;
Described replacement or unsubstituted C 2-C 60in heterocyclic aryl, at least one contains the ring texture of at least one in N, O and S atom.
2. compound according to claim 1, is characterized in that: described C 6-C 60aryl be selected from phenyl, naphthyl, xenyl, anthryl, dianthranide base, to tert-butyl-phenyl, 2,4-difluorophenyl, 4-(N, N-dimethyl amido) phenyl, 4-(N, N-phenylbenzene amido) phenyl, any one in 3-(N, N-phenylbenzene amido) phenyl, pyrenyl, naphthacenyl, phenanthryl, benzo phenanthryl, benzo anthryl, benzo pyrenyl and fluorenyl;
Described C 6-C 60aryloxy be selected from 4-Phenoxyphenyl, dibenzo [b, d] furans-2-base, dibenzo [b, d] furans-4-base, cumarone-2-base, cumarone-5-base and cumarone-7-base any one;
Described C 6-C 60arylthio be selected from dibenzo [b, d] thiophene-2-base, dibenzo [b, d] thiophene-4-base, 4-benzene sulfoxide group phenyl, 4-benzene sulfuryl phenyl, thionaphthene-2-base, thionaphthene-5-base and thionaphthene-7-base any one;
Described C 6-C 60virtue phosphino-be selected from 4-(two phenenyl phosphinyl) phenyl, 3-(two phenenyl phosphinyl) phenyl and dibenzo [b] phosphine oxide-5-(4-phenyl)-4-base any one;
Described C 6-C 60virtue is silica-based be selected from 4-(triphenyl is silica-based) phenyl, 4-(diphenyl methyl is silica-based) phenyl, 3-(triphenyl is silica-based) phenyl and 3-(diphenyl methyl is silica-based) phenyl any one;
Described C 6-C 60virtue boryl be selected from 4-(two (2,4,6-trimethylammonium) phenyl)-borine phenyl, dibenzo [b, d] borine-5-phenyl-4-base and triphenyl boryl any one.；
Described C 2-C 60heterocyclic aryl be selected from as shown in the formula any one in group shown in II-1 to formula II-15:
In described formula II-1 ~ II-15, Z 1, Z 2, Z 3independently be selected from hydrogen, deuterium hydrogen, halogen atom, hydroxyl, itrile group, nitro, amino, amidino groups, diazanyl, hydrazone group, carboxyl or its carboxylate salt, sulfonic group or its sulfonate, phosphate or its phosphoric acid salt, C 1-C 60alkyl, C 2-C 60thiazolinyl, C 2-C 60alkynyl, C 1-C 60alkoxyl group, C 3-C 60cycloalkyl group, C 3-C 60cycloalkenyl group, C 6-C 60aryl, containing C 1-C 10the C of alkyl 6-C 60aryl, replacement or unsubstituted C 6-C 60aryloxy, replacement or unsubstituted C 6-C 60arylthio, replacement or unsubstituted C 2-C 60any one in heterocyclic aryl;
The C of described replacement 6-C 60the C of aryloxy, replacement 6-C 60the C of arylthio and replacement 2-C 60in heterocyclic aryl, substituting group be selected from methyl, ethyl, the tertiary butyl, methoxyl group, cyano group, phenoxy group, halogen atom and containing 2 ~ 8 carbon atoms aliphatic group in any one;
X 1it is the integer of 1 ~ 4;
X 2it is the integer of 1 ~ 3;
X 3it is the integer of 1 ~ 2;
X 4it is the integer of 1 ~ 6;
X 5it is the integer of 1 ~ 5;
T 1for oxygen or sulphur atom.
3. compound according to claim 2, is characterized in that: compound shown in described formula I is for as shown in the formula any one in compound shown in I001 to formula I080:
4. the Organic Light Emitting Diode material containing compound shown in the arbitrary described formula I of claim 1-3.
5. shown in the arbitrary described formula I of claim 1-3, compound is preparing the application in Organic Light Emitting Diode material.
6. shown in the arbitrary described formula I of claim 1-3, compound is preparing the application in organic electroluminescence device as emitting layer material.
7. using compound shown in the arbitrary described formula I of claim 1-3 as the organic electroluminescence device of luminescent layer.
8. application according to claim 6 or device according to claim 7, is characterized in that: described organic electroluminescence device is made up of transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively.
9. application according to claim 8 or device, is characterized in that: the material forming described transparent substrate is glass or flexible substrate;
The material forming described anode layer is inorganic materials or organic conductive polymer; Wherein, described inorganic materials is specially tin indium oxide, zinc oxide, zinc tin oxide, gold and silver or copper; Described organic conductive polymer is specifically selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material forming described hole injection layer is TDATA, m-MTDATA or 2-TNATA:
The structural formula of described TDATA is as follows:
The structural formula of described m-MTDATA is as follows:
The structural formula of described 2-TNATA is as follows:
The material forming described hole transmission layer is NPB or TPD:
The structural formula of described NPB is as follows:
The structural formula of described TPD is as follows:
The material forming described organic luminous layer forms for compound shown in described formula I or by compound shown in described formula I and dopant material;
Wherein, described dopant material is compound shown in FIrpic, DMAC-DPS, BCz-DPS, PXZ-DPS, PTCz-DPS, BPT-DPS, DPVQ or DACQ;
The quality of compound shown in described formula I-and the mass ratio of described dopant material are 1-10:90;
Form the material of described electron transfer layer for compound shown in Liq, Alq3, Gaq3 or BAlq;
Wherein, the structural formula of compound shown in Liq is as follows:
The material forming described cathode layer is selected from any one or any alloys of two kinds of compositions in following element or the fluorochemical of following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
10. application according to claim 9 or device, is characterized in that: the thickness of described hole injection layer is 30-50nm; Be specially 30nm;
The thickness of described hole transmission layer is 5-15nm; Be specially 10nm;
The thickness of described organic luminous layer is 10-100nm; Be specially 40nm;
The thickness of described electron transfer layer is 10-30nm; Be specially 50nm;
The thickness of described cathode layer is 90-110nm, is specially 60nm.
CN201510991946.3A 2015-12-24 2015-12-24 Spirofluorene benzyl fluorescent material Pending CN105461611A (en)

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WO2019164341A1 (en) * 2018-02-23 2019-08-29 주식회사 엘지화학 Spiro compound and organic light-emitting device comprising same
CN108976134A (en) * 2018-09-28 2018-12-11 石家庄诚志永华显示材料有限公司 Spiral shell compound of fluorene class, material and organic electroluminescence device comprising the spiral shell compound of fluorene class
CN111269401A (en) * 2020-01-21 2020-06-12 惠州市亿纬新能源研究院 Polymer containing piperidine tertiary amine group, anion exchange polymer, and preparation methods and applications thereof
CN111269401B (en) * 2020-01-21 2023-12-05 惠州市亿纬新能源研究院 Polymer containing piperidine tertiary amine group, anion exchange polymer, and preparation method and application thereof
CN115286562A (en) * 2022-08-18 2022-11-04 青海大学 Benzoylation method of aromatic heterocyclic or aromatic amine compound containing rich electrons
CN115286562B (en) * 2022-08-18 2024-02-23 青海大学 Method for benzoylating aromatic heterocyclic or aromatic amine compound containing rich electron

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