CN106977527A - A kind of organic semiconductor compound and the organic electroluminescence device using the compound - Google Patents

A kind of organic semiconductor compound and the organic electroluminescence device using the compound Download PDF

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CN106977527A
CN106977527A CN201710276189.0A CN201710276189A CN106977527A CN 106977527 A CN106977527 A CN 106977527A CN 201710276189 A CN201710276189 A CN 201710276189A CN 106977527 A CN106977527 A CN 106977527A
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carbon atom
organic semiconductor
aromatic ring
light emitting
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CN106977527B (en
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洪海兵
李晓常
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GUANMAT OPTOELECTRONIC MATERIALS (JIANGXI) Inc
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Abstract

The invention discloses the organic electroluminescence device of a kind of organic semiconductor compound and the use compound, it is related to a kind of Organic Light Emitting Diode, it is by a negative electrode, one organic semiconductor layer between anode and negative electrode and anode is constituted, and is containing an organic semiconductor compound structural formula in described organic semiconductor luminescent layer：It is characterized in that described organic semiconductor is constituted by one containing the heteroaromatic with the phenyl ring and naphthalene nucleus for inhaling electrical nitrogen-atoms, the substituent for expanding ∏ conjugation or the linker L for expanding molecular weight are also associated with wherein on pyrrole ring nitrogen1.Using described organic semiconductor as luminescent layer application, luminous efficiency can be improved, extends device operational lifetime.

Description

A kind of organic semiconductor compound and the organic electroluminescence device using the compound
Technical field
The present invention relates to luminous organic material and its in the application of organic luminescent device, and in particular to organic semiconductor conduct Luminescent layer application, can improve luminous efficiency, extend device operational lifetime.
Background technology
Organic semiconducting materials belong to novel optoelectronic materials, and its broad scale research originates from 1977 by Hideki Shirakawa, A.Heeger and A.McDiamid are found that doped polyacetylene of the conductive car up to copper level jointly.Then, KodaK public affairs in 1987 C.Tang of department etc. has invented organic molecule light emitting diode (OLED), and nineteen ninety Cambridge University R.Friend and A.Holmes has invented polymer LED P-OLED, and S.Forrest in 1998 and M.Thomson has invented efficiency Higher Phosphorescent LED P HOLED.It can obtain numerous in variety because there is organic semiconducting materials structure easily to adjust, Can be with adjustable, or even the inexpensive benefit as being processed plastic sheeting adds organic semiconductor in conductive film, electrostatic is multiple The crowd such as print, photovoltaic solar cell application, OTFT logic circuit, and organic light emission OLED FPD and illumination Using three scientists of Bai Chuan-Heeger-McDiamid obtained Nobel chemistry Prize in 2000.
As the Organic Light Emitting Diode of flat panel display of future generation, the requirement of organic photoelectric semiconductor has：1. height is luminous Efficiency；2. excellent electronics and hole stability；3. suitable glow color；4. excellent film forming processability.In principle, big portion Divide conjugacy organic molecule (including star beam), conjugacy polymer, and the organic heavy metal containing conjugacy chromophore part Complex compound, which has, possesses electroluminescence performance, applies in all kinds of light emitting diodes, such as organic molecule light emitting diode (OLED), Polymer organic LED (POLED), Phosphorescent light emitting diode (PHOLED), organic hot activation delayed fluorescence TADF OLED.Organic hot activation delayed fluorescence material can allow the electronics in triplet efficiently return to list by inverse intersystem crossing Weight state, and return ground state from singlet state transition and send fluorescence.PHOLED and TADF OLED quantum efficiency and luminous efficiency is one As 3~4 times of fluorescence OLED material, therefore decrease the heat of generation, increase the competitiveness of OLED display boards.This point There is provided generally OLED to show or illuminate to surmount LCD to show and conventional light source possibility.
Phosphorescent OLED material is as two tooth chelands, with metallic element by the organic light emission group for containing certain conjugacy Ring metal-ligand complex compound is formed, (such as ultraviolet light to excite) or electric charge injection (electricity to the excite) condition under high energy light photograph Under, because ring metal-ligand charge transfer (MLCT) turns into exciton, then revert to ground state and cause to light.General organic In semi-conducting material, according to Hund's rules, the energy of triplet can be less than singlet state, band difference (△ Est) be typically 0.5eV or More than so that the electronics in triplet there should be no return to singlet state substantially.And in TADF materials, by MOLECULE DESIGN so that The overlapping reduction of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in molecular orbit, prepares triplet state and list Line state energy level difference only has 0.1eV or following fluorescent material, and the HOMO and LUMO of molecule are overlapping fewer, and △ E are smaller, make electricity Son can cross singlet from the inverse system of triplet state and obtain and equally reach 100% electricity to luminous effect similar to phosphorescence is luminous Rate.The example of material reported is 2,6- dicyanos -1,3 of green light, 4,5- tri- carbazole benzene.
The injection of electric charge is that negative electrode is applied by the way that after anode applies positive voltage, hole is injected from anode in OLED Plus inject electronics after negative voltage, respectively through electron transfer layer and transporting holes layer, at the same into emission layer bulk material or In material of main part, the minimum end that electronics is eventually entered into light-emitting dopant accounts for molecular orbit (LUMO), and hole enters luminescent dopant Highest occupied molecular orbital(HOMO) (HOMO) in agent and form excitation state luminescent dopant agent molecule (exciton state).Exciton state is returned to base Along with transmitting luminous energy after state, it launches energy gap (the HOMO-LUMO energy levels that luminous energy wavelength just correspond to light emitting molecule dopant Difference).
The existing heavy metal organic ligand complex compound much reported, is influenceed by heavy metal and enhances spin(-)orbit and make With so that should weaker phosphorescence become very strong and excellent phosphorescent emissions be presented.Three (phenylpyridines) of such as green light according to (III) complex compound, referred to as Ir (PPY) are coordinated3, it is with structural formula：
The FirPic of transmitting blue light has following structural formula：
Main part 4 therein, 6- difluoro-benzene yl pyridines dominate glow color.Launch three (octyl quinoline) of feux rouges Coordinate complex compound according to (III), be with excellent efficient transmission performance (Adv.Mater.19,739 (2007)) its structural formula：
Luminescent layer is usually semiconductor body material (or the main body for having more high level by a small amount of luminescent material incorporation one Material) middle composition.Recent study shows that, for same luminescent material or a kind of colour light emitting device, bulk material is not With different device light emitting efficiency and working life can be caused.Therefore, it is always influence organic light emission to develop new bulk material The important topic of diode practical application.For ease of hole, the injection of electronics, preferable bulk material should possess the hole of balance With electron injection and transmittability.To reach this purpose, there are many improved bulk materials to appear in the newspapers.V.Adamocich(US 2006/0280965) bulk material that carbazole is connected with triphenylene is disclosed.C.Adachi (WO 2012/114745) is disclosed The bipolar body material being connected using pyridine with triphenylene.A.Dyatkin (US 2012/0256169) is disclosed by benzo thiophene The bipolar body material that fen, phenyl and indolepyridinium are constituted.Patent US2016002802 and WO2015037965 are disclosed A kind of bisbenzothiazole fusion carbazole is remarkably improved luminous effect with inhaling the material of main part that electrical heteroaromatic is linked, the compound Rate；Patent (CN201310699039.2 and CN2017100348155) discloses a kind of 3- naphthopyridines benzazolyl compounds as double Polarity material of main part is in the application of organic luminous layer, and the compound is remarkably improved luminous efficiency compared to CBP, extends device Working life LT90%.
The content of the invention
Design herein has synthesized the fusion aryl-heterocyclic unit by core of 3- naphthopyridines indoles and has constructed a series of bipolarity properties Compound, make it have the good film forming characteristics of 3- naphthopyridine indoles and high heat endurance again have pyridine indole structure compared with The electron hole transmission performance of high triplet and good balance.In addition, by miscellaneous in 3- naphthopyridines indoles and aryl The periphery of ring introduces the suction electricity or power supplying groups of varying number, not only with lower sublimation temperature, and being capable of regulation The electron transport ability and orbital energy level of compound.So that the cavity transmission ability and electron transport ability of such bipolarity compound Mutually balance, is lighted with expanding exciton high efficiency composition in luminescent layer, improves device performance.
The present invention provides a kind of bipolarity organic semiconductor compound as bulk material, it is characterized in that using pyrroles simultaneously Electrical nitrogen atom ring is inhaled in fusion and electron-donating double fusion rings are used as new bipolar structural unit, described organic semiconductor Compound has 3.4~2.0eV of band gap, and with following general molecular formula (I)：
It is characterized in that X1-X4For C or N, and X1-X4It is N atoms at least containing one；
It is characterized in that L1For the substituent on pyrroles's nitrogen-atoms of connection fusion ring, it independently is：One carbon atom is less than 12 Alkyl；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 heteroaromatic or substitution heteroaromatic；One Carbon atom is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon atom linker；One carbon atom is small In 48 phosphorus atoms linker；One crosslinkable vinyl；
It is characterized in that R1~2Respectively H, D, F, Cl, OH, OR, SR ,-NR2,CN,CO2R, COR, carbon number are 1~48 Alkyl, fluoro-alkyl, aralkyl, Heterocyclylalkyl, a heteroaromatic or an aromatic ring, a crosslinkable vinyl；M, n are the 1 of permission To multiple substitution radixes；
It is characterized in that Y is independently expressed as O, S, alkyl C (R3R4), silylation Si (R3R4), nitrogen base N-L2, wherein R3,R4, L2It independently is：One carbon atom is less than 12 alkyl；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 heteroaromatic or substitution heteroaromatic；One carbon atom is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 Silicon atom linker；One carbon atom is less than 48 phosphorus atoms linker；One crosslinkable vinyl；It is characterized in that described Bipolarity organic semiconductor compound has can 3.4~2.0eV of band.
Without prejudice under this patent ambit, described organic semiconductor compound structure is from following structure Any one：
Structure according to above-mentioned formula, L1Structure can include following group：
According to the scope of claim, examples detailed above compound C1~C195 and D1~D33 compounds can be single or multiple Substitution, substituent is chosen as：H,D,F,Cl,OH,OR,SR,-NR2,CN,CO2R, COR, alkyl, fluorine of the carbon number for 1~12 Substituted alkyl, aralkyl, Heterocyclylalkyl, a heteroaromatic or an aromatic ring, wherein aromatic ring or heteroaromatic are optionally substitution one or many Individual substituent.
Structure according to above-mentioned formula, specifically including but not limited to following structure：
The described organic semiconductor compound of this patent can be obtained by various ways, and a typical multistep reaction is anti-as follows Answer shown in formula 1：
Reaction equation 1
According to scope, OLED is made in order to more be applicable solution, easy dissolving is on the one hand obtained, it is another After aspect film forming again can by chemical crosslinking obtain it is insoluble, do not melt, be easy to lasting use solution that multilayer OLED structure is made.Cause This, the present invention also provides the organic semiconductor compound that a kind of band is crosslinked functional group.There are many chemical groups all to possess crosslinking work( Can, wherein being typically included in heating or ultraviolet light shines lower crosslinked group, for example, it is connected to following comprising second on phenyl ring Alkenyl (A), acrylic (B) and trifluoro vinyl (C)：
Logical formula (I) definition, required for thering are various structures to meet the present invention, wherein including but not limited to such as Under cross-linking general structure：
It is characterized in that X1-X4For C or N, and X1-X4It is N atoms at least containing one；
It is characterized in that L1For the substituent on pyrroles's nitrogen-atoms of connection fusion ring, it independently is：One carbon atom is less than 12 Alkyl；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 heteroaromatic or substitution heteroaromatic；One Carbon atom is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon atom linker；One carbon atom is small In 48 phosphorus atoms linker；
It is characterized in that R1~2Respectively H, D, F, Cl, OH, OR, SR ,-NR2,CN,CO2R, COR, carbon number are 1~48 Alkyl, fluoro-alkyl, aralkyl, Heterocyclylalkyl, a heteroaromatic or an aromatic ring；M, n arrive multiple substitution radixes for the 1 of permission；
It is characterized in that Y is independently expressed as O, S, alkyl C (R3R4), silylation Si (R3R4), nitrogen base N-L2, wherein R3,R4, L2It independently is：One carbon atom is less than 12 alkyl；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is small In 48 heteroaromatic or substitution heteroaromatic；One carbon atom is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon atom linker；One carbon atom is less than 48 phosphorus atoms linker；One crosslinkable vinyl；It is characterized in that described Bipolarity organic semiconductor compound have can band 3.4~2.0eV.
The material of main part with crosslinked group is more than 160 in heating-up temperature in luminescent layer in described Organic Light Emitting Diode DEG C, insoluble cross-linked network structure is formed, such as typical reaction is：
According to logical formula (II), (III), (IV), luminescent layer material of main part or body material in described Organic Light Emitting Diode Material includes following structural formula：
In applied to Organic Light Emitting Diode, a bulk material is generally mixed to form luminescent layer with a luminescent material.It is mixed Spin coating in solution, spraying or solution impact system can be dissolved in by vacuum co evaporation plated film, or by mixing by synthesizing film.The present invention's Contain described bulk material in the luminescent layer of luminescent device, sent out with a luminescent material by coevaporation or solution-coating method formation Photosphere, its thickness is 5~50 nanometers.In one case, luminescent material is red, can be specifically：
In another case, luminescent material is green：
In another case, luminescent material is blueness：
In another case, luminescent material is TADF heat shock delayed fluorescence materials, such as a variety of feux rouges or green light material, The example of material of report is 2,6- dicyanos -1,3 of green light, 4,5- tri- carbazole benzene.
To reach excellent device performance, a flourishing Organic Light Emitting Diode will also include a variety of other organic partly lead Body material layer, Fig. 1 is an illustrative device structure., can optional hole injection layer HIL, such as blue or green blue (CuPc) on anode Or other containing fragrant ammonia compound (Appl.Phys.Lett., 69,2160 (1996),
Similarly, between hole injection layer and emission layer EML, a hole transmission layer HTL also may be selected, 4 are such as used, 4 '-bis- [N- (1- naphthyls)-N- phenylaminos] biphenyl (α-NPD),
For the injection in balance electronic and hole, improve luminous efficiency, can an optional exciton (exciton) barrier layer BL, Example for barrier material is 2,9- dimethyl -4,7- diphenyl -1,10- phenanthroline (BCP), and its structure is：
Between barrier layer and negative electrode, also usually using electron transfer layer ETL and electron injecting layer EIL.Electron transfer layer Material can optional metals quinoline compound, such as three-(8- hydroxyls) aluminium (Alq3) , oxadiazoles or triazole types.Alq3 structure is：
Electron injecting layer EIL is typically the relatively low metal Lithium of work content, or its compound such as LiF, 8- hydroxyls Lithium (Liq) etc..
Organic Light Emitting Diode according to this patent scope, it is characterized in that described Organic Light Emitting Diode is sometimes Co-host that can also be containing an increase electronics or Hole injection capacity in acquisition higher performance light emitting diode, luminescent layer Material, namely hybrid agent material is used, the proportioning of wherein co-host material and primary body material is 5-45%.As green Color and red phosphorescent OLED, the material of main part that any triplet is more than 2.0eV all can be as luminescent material of the invention OLED application.It is preferred that co-host material have electron-donating material DBPP：
Co-host material can also be following electronegativity material MCBP：
Therefore, OLED luminescent devices are a complicated sandwich constructions, and Fig. 1 is a typical construction, but is not uniquely should Use structure.Regardless of structure, all comprising a negative electrode, an anode and one layer of organic semiconductor layer, wherein organic semiconductor The general thickness of layer is 50~250 nanometers, and preferably gross thickness is 80~180 nanometers.
The invention is characterised in that described luminescent device is the organic luminescent device of an efficient stable, launch wavelength is 450 ~630nm, applied to organic light emission panel display screen, such as Mobile phone screen, personal electric device such as i-Pack screens, TV screen, computer Screen etc..The semiconductor bipolar material of the present invention can be used for plate lighting.To reach white-light illuminating, it is necessary to use two kinds Or the OLED of three kinds of different colours is mixed into white-light illuminating device by longitudinal stack, or level.For example, being had using a blueness Machine luminescent device (445~485nm of launch wavelength) and orange red organic luminescent device (570~610nm of a launch wavelength) institute group Into two knot white light parts.More complicated white light emitting device is by red (570~640nm), green (505~565nm) and indigo plant (445 ~485nm) three knot white light parts composition.
The beneficial effects of the invention are as follows using the bulk material of the present invention, be conducive to improving OLED luminescent properties, obtain high Effect, more stable luminescent properties.
Brief description of the drawings
Fig. 1 is organic LED structure schematic diagram.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, with reference to examples of implementation to this The embodiment of invention is described in detail.Many details are elaborated in the following description to fully understand The present invention.But the invention can be embodied in many other ways as described herein, those skilled in the art can be with Similar popularization is done in the case of without prejudice to intension of the present invention.Therefore the present invention is not limited by following public specific embodiment System.
Embodiment 1：Compound C151's is synthetically prepared
Intermediate 1-1 synthesis：
1. in 1000mL three-necked bottle, sequentially add 5- bromobenzenes simultaneously [B] naphtho- [1,2-D] thiophene 62.6g, connection boric acid frequency That alcohol ester 60g, anhydrous acetic acid potassium 50g, Pd2(dba)33.6g, S-Phos 4g and solvent DMF 500mL, N2Displacement three times, heating To flowing back, stop after reaction 16h.
2. being cooled to room temperature, filter, water is counter to be precipitated, and obtained solid passes through pillar layer separation (EA：DCM=1:20) respectively Receive target white solid product 38g (51%), M1/ z=360, HPLC>99.3%.
Intermediate 1-2 synthesis：
1. in 1000mL three-necked bottle, sequentially add intermediate 1 38g, 3- nitro -2- bromopyridine 21.4g, tricresyl phosphate Potassium 65g, toluene 400mL, H2O 150mL, Pd2(dba)32.0g, S-Phos2g, N2Displacement 3 times, is heated to back flow reaction and stays overnight.
2. filtering, methanol is counter to be precipitated, pillar layer separation, is spin-dried for producing product 31.7g, M1/ z=356, yield：91%, HPLC>99%.
Intermediate 1-3 synthesis：
1. in 250mL three-necked bottle, sequentially addIntermediate 231.7g, triethyl phosphite 200mL, N2Displacement three It is secondary, stop after being warming up to backflow, reaction 8h.
2. being cooled to room temperature, solvent is fallen in concentration, and obtained solid passes through pillar layer separation (EA：Dichloromethane=1:20) divide Target yellow solid product 26.0g (90%), M are not received1/ z=324, yield：90%, HPLC>99.5%.
The synthesis of final product：
1. in 100mL three-necked bottle, sequentially add the bromo- 4- phenylquinazolines 0.60g of intermediate 3 0.65g, 2-, copper powder 0.3g, 18-crown-6 0.5g, Anhydrous potassium carbonate 5.1g and solvent o-dichlorohenzene 50mL, N2Displacement three times, is warming up to backflow, React and stop after 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is yellow that target is received respectively Color solid product 0.65g (62%), M1/ z=528, HPLC>99.3%.
Embodiment 2：Compound C149's is synthetically prepared
1. in 100mL three-necked bottle, sequentially add chloro- 4, the 6- diphenyl triazine 1.02g of intermediate 3 0.65g, 2-, copper Powder 0.3g, 18-crown-6 0.5g, Anhydrous potassium carbonate 5.1g and solvent o-dichlorohenzene 50mL, N2Displacement three times, is warming up to back Stop after stream, reaction 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is white that target is received respectively Color solid product 0.72g (69%), M1/ z=555, HPLC>99.3%.
Embodiment 3：Compound C157's is synthetically prepared
1. in 100mL three-necked bottle, sequentially add intermediate 3 0.65g, 2- (3- bromophenyls) -4,6- diphenyl triazines 1.02g, copper powder 0.3g, 18-crown-6 0.5g, Anhydrous potassium carbonate 5.1g and solvent o-dichlorohenzene 50mL, N2Displacement three times, rises Temperature stops to flowing back after reaction 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is white that target is received respectively Color solid product 0.65g (52%), M1/ z=631, HPLC：98.9%.
Embodiment 4：Compound C166's is synthetically prepared
1. in 100mL three-necked bottle, sequentially add intermediate 3 0.65g, 2- (- 4- bromophenyls) -1- phenyl-benzo miaow Azoles 1.34g, Pd2(dba)30.1g, S-phos 0.2g, Anhydrous potassium carbonate 1.4g and solvent toluene 50mL, N2Displacement three times, heating To flowing back, stop after reaction 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is white that target is received respectively Color solid product 0.36g (31%), M1/ z=592, HPLC：99.7%.
Embodiment 5：Compound C173's is synthetically prepared：
Intermediate 5-1 synthesis：
1. in 1000mL three-necked bottle, sequentially add 3- nitro -2- bromopyridines 20.3g, 1- naphthalene boronic acids 19g, sodium carbonate 24g, Pd2(dba)32.1g, S-Phos3.2g, solvent toluene 300mL and water 100mL, N2Displacement three times, is warming up to backflow, reacts Stop after 16h.
2. being cooled to room temperature, filter, point liquid, concentration, methanol mashing, the solid being filtrated to get passes through dichloromethane and oil The mixed solvent washing of ether, receives target white solid product 20g (80.5%), M1/ z=250, HPLC：99.6%.
Intermediate 5-2 synthesis：
1. in 500mL three-necked bottle, sequentially adding intermediate 5-1 20g, anhydrous acetic acid 300mL, backflow drop is warming up to Stop after liquid feeding bromine 5mL, reaction 16h.
2. being cooled to room temperature, filter, methanol mashing, the solid being filtrated to get is molten by the mixing of dichloromethane and petroleum ether Agent brush short column of silica gel, concentration, receives target yellow solid product 23.36g (92%), M1/ z=329, HPLC>99.1%.
Intermediate 5-3 synthesis：
1. in 250mL three-necked bottle, intermediate 5-223.3g, o-dichlorohenzene 150mL, triphenylphosphine 50g are sequentially added, It is warming up to after back flow reaction 4h and stops.
2. 2/3 solvent is fallen in vacuum distillation, cooling, petroleum ether adds anti-precipitation, and the solid being filtrated to get passes through dichloromethane The mixed solvent brush short column of silica gel of alkane and petroleum ether, concentration, receives target yellow solid product 17.8g (85%), M1/ z= 297, HPLC>99.0%.
Intermediate 5-4 synthesis：
1. in 250mL three-necked bottle, sequentially add intermediate 5-317.8g, o-dichlorohenzene 150mL, 18-crown- 622g, copper powder 4.5g, Anhydrous potassium carbonate 25g, are warming up to after back flow reaction 24h and stop.
2. being cooled to room temperature, filter, collect filtrate, 4/5 solvent is fallen in vacuum distillation, cool down, petroleum ether adds anti-precipitation, The solid being filtrated to get receives target yellow solid by dichloromethane and the mixed solvent brush short column of silica gel of petroleum ether, concentration Product 16.1g (72%), M1/ z=373, HPLC>99.0%.
Intermediate 5-5 synthesis：
1. in 250mL three-necked bottle, sequentially add intermediate 5-4 11g, connection boric acid pinacol ester 9.1g, anhydrous acetic acid Potassium 9.8g, PdCl2(DPPF)21.5g and solvent dioxane 200mL, N2Displacement three times, stops after being warming up to backflow, reaction 16h Only.
2. being cooled to room temperature, filter, water is counter to be precipitated, and obtained solid passes through pillar layer separation (EA：DCM=1:20) respectively Receive target white solid product 10.2g (82%), M1/ z=420, HPLC>98.2%.
Intermediate 5-6 synthesis：
1. in 250mL three-necked bottle, intermediate 5-510.2g, o-bromonitrobenzene 4.9g, sodium carbonate 5.3g are sequentially added, Pd(PPh3)41.0g, solvent DME100mL and water 50mL, N2Displacement three times, stops after being warming up to backflow, reaction 16h.
2. being cooled to room temperature, filter, point liquid, concentration, methanol mashing, the solid being filtrated to get passes through dichloromethane and oil The mixed solvent washing of ether, receives target yellow solid product 7g (70%), M1/ z=415, HPLC>99.6%.
Intermediate 5-7 synthesis：
1. in 250mL three-necked bottle, sequentially adding intermediate 5-67g, o-dichlorohenzene 80mL, triphenylphosphine 20g, heat up Stop after to back flow reaction 4h.
2. 2/3 solvent is fallen in vacuum distillation, cooling, petroleum ether adds anti-precipitation, and the solid being filtrated to get passes through dichloromethane The mixed solvent brush short column of silica gel of alkane and petroleum ether, concentration, receives target yellow solid product 5.56g (85%), M1/ z= 383, HPLC>99.0%.
The synthesis of final product：
1. in 100mL three-necked bottle, chloro- 4, the 6- diphenyl triazine 1.02g of intermediate 5-70.77g, 2- is sequentially added, Copper powder 0.3g, 18-crown-6 0.5g, Anhydrous potassium carbonate 5.1g and solvent o-dichlorohenzene 50mL, N2Displacement three times, is warming up to back Stop after stream, reaction 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is yellow that target is received respectively Color solid product 0.69g (56%), M1/ z=614, HPLC>99.7%.
Embodiment 6：Compound C172's is synthetically prepared
1. in 100mL three-necked bottle, sequentially add intermediate 5-70.77g, 2- (3- bromophenyls) -4,6- diphenyl three Piperazine 1.02g, copper powder 0.3g, 18-crown-6 0.5g, Anhydrous potassium carbonate 5.1g and solvent o-dichlorohenzene 50mL, N2Displacement three times, Stop after being warming up to backflow, reaction 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is yellow that target is received respectively Color solid product 0.94g (68%), M1/ z=690.
Embodiment 7：Compound C161's is synthetically prepared
1. in 100mL three-necked bottle, sequentially add intermediate 5-70.77g, 2- (- 4- bromophenyls) -1- phenyl-benzo Imidazoles 1.34g, Pd2(dba)30.1g, S-phos 0.2g, Anhydrous potassium carbonate 1.4g and solvent toluene 50mL, N2Displacement three times, rises Temperature stops to flowing back after reaction 16h.
2. being cooled to room temperature, filter, obtained solid passes through pillar layer separation (PE：DCM=1:1) it is white that target is received respectively Color solid product 0.59g (45%), M1/ z=651, HPLC>99%.
Following each cross-linking material of main part compound, listed compound are prepared according to chemical reaction formula principle respectively The fragment that molecular weight and molecule have is demonstrated by mass spectrum, table 1 below is specifically shown in：
Table 1：Compound synthesis and sign
The device application example 1 of embodiment 8.
In a base vacuum up to 10-5In the Multisource evaporation OLED Preparation equipments of handkerchief, using following device mechanism：ITO/ m-TDATA/NPD/Host:5% light-emitting dopant 10%/TPBi /LiF/ Al, using different Host OLED luminescent devices to compare.The vacuum moulding machine speed of wherein each organic layer and electrode in when Between be listed in table 2.
Table 2:Contrast material of main part structure
Table 3：OLED preparation condition (wt concentration 9% of being adulterated in luminescent layer)
Material Deposition velocity (angstroms per second) Thickness control (angstrom) Required time (second)
HIL：m-TDATA 0.5 100 200
HTL：NPD 2.0 400 200
EML:Host/Dopant 10% 1.5 300 200
ETL:TPBi 1.0 200 200
EIL:LiF 0.5 10 20
Al 5.6 1000 180
All OLEDs being made are tested and accelerated aging test after encapsulation, as a result summarize such as table 4.
Table 4：OLED performance and accelerated ageing result (under room temperature 1000nits)
Table 4 illustrates that the material of main part exemplified by the compounds of this invention is applied to known green glow (emission wavelength 512nm), feux rouges (emission wavelength 619nm) doping illuminating OLED, which has, is obviously improved luminescent properties, than existing material of main part comparative compound Ref.1, comparative compound Ref.2, comparative compound Ref.3 have higher luminous efficiency LE (lifting amplitude 20% with On), and driving voltage is lower, accelerated life LT90%Extended for more than 50% time；And compound (the 3- naphthalene pyrroles of the present invention Pyridine indoles connects pyridine benzazolyl compounds) there is unexpected current efficiency and longer aging life-span.Find simultaneously, the present invention Compound C173 prepared device 13 and 14 mixed with MCBP co-host materials there is excellent current efficiency and longer Aging life-span.
The device application example 2 of embodiment 9.
On an electro-conductive glass ITO surfaces, after solvent, plasma cleaning, solution spin coating PEDOT conducting polymers are used as sky Cave implanted layer, using poly- (the heptane fluorenes of triphenylamine -9,9- bis-), solution spin-coating film is as hole transmission layer, then using 2% Material of main part/light-emitting dopant green glow Ir (Me-PPY)3Or feux rouges Ir (piq-hex)3(weight of doping concentration 8%) mixed solution After spin coating, handled 30 minutes to 160 DEG C through heated under nitrogen, turn into its film and do not melt insoluble；Secondly using solution spin coating one Layer TPBiIt is last in a base vacuum up to 10-5In the Multisource evaporation OLED Preparation equipments of handkerchief, evaporation electronics note Enter a layer LiF Prepare OLED.Using different Host OLED luminescent devices to compare.
Table 5. contrasts known materials material of main part：
All OLEDs being made carry out test I-V-L and accelerated aging test after encapsulation, as a result summarize such as table 6：
Table 6：Solution prepares OLED performance and accelerated ageing result (under room temperature 1000nits)
Table 6 illustrates that the material of main part exemplified by the compounds of this invention is applied to known green glow (emission wavelength 520nm), feux rouges (emission wavelength 620nm) doping illuminating OLED, which has, is obviously improved luminescent properties, than existing material of main part DBCz and Ref.3 Corresponding comparative device A, B, C and D has higher luminous efficiency LE (lifting amplitude is more than 30%), and driving voltage is more It is low, accelerated life LT90%Extended for more than 40% time；Meanwhile, compound D-8 and D-20 and MCBP of the invention is aided in The prepared device 13 and 14 of material of main part mixing has excellent current efficiency and longer aging life-span.
It is indicated above, by suction electricity or power supply that varying number is introduced in the periphery of 3- naphthopyridines indoles and aryl-heterocyclic Group, not only with lower sublimation temperature, and is capable of the electron transport ability and orbital energy level of modulating compound.So that this The cavity transmission ability and electron transport ability of class bipolarity compound are mutually balanced, and are efficiently answered in luminescent layer with expanding exciton Close luminous, improve device performance, be conducive to improving charge balance injection and stability of photoluminescence, can especially obtain can solution film forming Then by being chemically crosslinked luminescent layer, then can continuously reuse solution film forming electron transfer layer ET, be conducive to obtain it is low into Originally, large area solution manufacture OLED.
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention.Appoint What those skilled in the art, without departing from the scope of the technical proposal of the invention, all using the skill of the disclosure above Art content makes many possible variations and modification to technical solution of the present invention, or is revised as the equivalent embodiment of equivalent variations. Therefore, every content without departing from technical solution of the present invention, the technical spirit according to the present invention is to made for any of the above embodiments What simple modification, equivalent variation and modification, is still within the scope of the technical scheme of the invention.

Claims (10)

1. a kind of Organic Light Emitting Diode, it is characterized in that the Organic Light Emitting Diode by partly constituting as follows：
(a) negative electrode
(b) anode
(c) a sandwich organic semiconductor luminescent layer between negative electrode and anode, it is characterised in that described organic semiconductor hair Contain a kind of organic semiconductor compound in photosphere, its chemical structure of general formula is：
It is characterized in that X1-X4For C or N, and X1-X4It is N atoms at least containing one；
It is characterized in that L1For the substituent on pyrroles's nitrogen-atoms of connection fusion ring, it independently is：One carbon atom is less than 12 alkane Base；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 heteroaromatic or substitution heteroaromatic；One carbon is former Son is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon atom linker；One carbon atom is less than 48 Phosphorus atoms linker；One crosslinkable vinyl；
It is characterized in that R1~2Respectively H, D, F, Cl, OH, OR, SR ,-NR2,CN,CO2R, COR, carbon number are 1~48 alkyl, Fluoro-alkyl, aralkyl, Heterocyclylalkyl, a heteroaromatic or an aromatic ring, a crosslinkable vinyl；M, n arrive multiple for the 1 of permission Replace radix；
It is characterized in that Y is independently expressed as O, S, alkyl C (R3R4), silylation Si (R3R4), nitrogen base N-L2, wherein R3,R4,L2Solely It is on the spot：One carbon atom is less than 12 alkyl；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 Heteroaromatic or substitution heteroaromatic；One carbon atom is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon Atom linker；One carbon atom is less than 48 phosphorus atoms linker；One crosslinkable vinyl；
It is characterized in that described bipolarity organic semiconductor compound has 3.4~2.0eV of energy band.
2. Organic Light Emitting Diode according to claim 1, it is characterised in that described organic semiconductor compound be comprising But it is not limited to any one in following structure：
3. organic semiconductor compound according to claim 1, it is characterised in that described L1For including but not limited to as follows Any one of structure：
4. organic semiconductor compound according to claim 1, it is characterised in that described organic semiconductor compound bag Contain but be not limited to any one of following structure：
5. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in described Organic Light Emitting Diode L1 in material of main part compound is connected with the unit of at least one crosslinked group, and described crosslinked group is selected from vinyl, propylene Sour fat or trifluoro vinyl；With following structural formula：
It is characterized in that X1-X4For C or N, and X1-X4It is N atoms at least containing one；
It is characterized in that L1For the substituent on pyrroles's nitrogen-atoms of connection fusion ring, it independently is：One carbon atom is less than 12 alkane Base；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 heteroaromatic or substitution heteroaromatic；One carbon is former Son is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon atom linker；One carbon atom is less than 48 Phosphorus atoms linker；
It is characterized in that R1~2Respectively H, D, F, Cl, OH, OR, SR ,-NR2,CN,CO2R, COR, carbon number are 1~48 alkyl, Fluoro-alkyl, aralkyl, Heterocyclylalkyl, a heteroaromatic or an aromatic ring；M, n arrive multiple substitution radixes for the 1 of permission；
It is characterized in that Y is independently expressed as O, S, alkyl C (R3R4), silylation Si (R3R4), nitrogen base N-L2, wherein R3,R4,L2Solely It is on the spot：One carbon atom is less than 12 alkyl；One carbon carbon atom is less than 48 aromatic ring or substitution aromatic ring；One carbon atom is less than 48 Heteroaromatic or substitution heteroaromatic；One carbon atom is less than 48 fusion aromatic ring or substitution fusion aromatic ring；One carbon atom is less than 48 silicon Atom linker；One carbon atom is less than 48 phosphorus atoms linker；
It is characterized in that described bipolarity organic semiconductor compound has 3.4~2.0eV of energy band.
6. Organic Light Emitting Diode according to claim 5, it is characterized in that luminescent layer in described Organic Light Emitting Diode Material of main part is more than 160C in heating-up temperature, forms insoluble cross-linked network structure, including but not limited to：
Or：
Or：
7. Organic Light Emitting Diode according to claim 5, it is characterized in that luminescent layer in described Organic Light Emitting Diode Material of main part includes following structural formula：
8. Organic Light Emitting Diode according to claim 1, it is characterized in that the sheet in described organic semiconductor luminescent layer Body material, mixture luminescent layer is formed with dopant fluorescence luminescent material, wherein described organic semiconductor compound is used as this Body material weight content is 60%~99%, and dopant luminescent material weight content is 1%-40%；Described organic semiconductor Light emitting layer thickness is 2~60 nanometers.
9. Organic Light Emitting Diode according to claim 1, it is characterized in that the sheet in described organic semiconductor luminescent layer Body material, forms mixture luminescent layer, wherein described bipolarity organic semiconductor compound with dopant phosphorescent light-emitting materials It is 60%~99% as bulk material weight content, dopant luminescent material weight content is 1%~40%；Described is organic Semiconductor light emitting layer thickness is 2~60 nanometers.
10. Organic Light Emitting Diode according to claim 1, it is characterized in that the sheet in described organic semiconductor luminescent layer Body material, forms mixture luminescent layer, wherein described bipolarity organic semiconductor with dopant heat shock delayed luminescence material Compound is 60%~99% as bulk material weight content, and dopant luminescent material weight content is 1%~40%；Described Organic semiconductor light emitting layer thickness is 2~60 nanometers.
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