CN103467447B - One class electroluminescent organic material and applying in the devices - Google Patents
One class electroluminescent organic material and applying in the devices Download PDFInfo
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- CN103467447B CN103467447B CN201310398299.6A CN201310398299A CN103467447B CN 103467447 B CN103467447 B CN 103467447B CN 201310398299 A CN201310398299 A CN 201310398299A CN 103467447 B CN103467447 B CN 103467447B
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- quinoline derivatives
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Abstract
The invention discloses a class electroluminescent organic material and apply in the devices, wherein, the general formula of molecular structure of described quinoline derivatives is:
wherein, W, Z, X, Y are the one in carbon atom or nitrogen-atoms; Ar
1group to be carbonatoms be 6 ~ 14 aryl, Ar
2group to be carbonatoms be 12 ~ 30 aromatic heterocyclic radical.Containing quinoline derivatives, there is high luminous efficiency, high luminous efficiency shows that this compound can be used as luminescent material or light emitting host material, be applied in organic electroluminescence device, its manufacturing cost is lower, extend the life-span of organic electroluminescence device, reduce the manufacturing cost of organic electroluminescence device.
Description
Technical field
The present invention relates to organic photoelectrical material field, particularly relate to a class electroluminescent organic material and apply in the devices.
Background technology
Organic electroluminescent (EL) device (hereinafter, simply referred to as " organic EL device ").Generally be made up of two opposed electrodes and at least one deck organic luminescent compounds be inserted between these two electrodes.Electric charge is injected in the organic layer formed between the anode and cathode, to form electronics and hole pair, makes the organic compound with fluorescence or phosphorescent characteristics create light emission.
Research for organic EL Material applies the observation of high current/voltage from nineteen fifty Bernose to the macromolecule membrane containing organic pigment to obtain.Nineteen sixty-five, people's Late Cambrian such as Pope Electroluminescence Properties of anthracene single crystal, this is the first electro optical phenomenon of organic compound.1987, the people such as the Tang of Kodak found, even if the organic electroluminescence device with separation function lamination formed by organic materials also can provide 1000cd/cm under the low voltage of 10V or less
2or higher high brightness.
Because in organic materials, the mobility in hole is significantly higher than electronic mobility, so can more effectively to luminescent layer transporting holes and electronics when using suitable hole transmission layer and electron transfer layer.In addition, when the hole density in luminescent layer and electron density balance, luminous efficiency can be improved.
When electronics, hole combine in organic molecule again, can be different because of electron spinning symmetric mode, produce the form of two kinds of excited state.Be the singlet excited form formed by the ground state electron of non-spin symmetry, it can release energy with the form of fluorescence and get back to ground state; Another kind is the triplet excited state form formed by the ground state electron of spin symmetry, gives off energy get back to ground state with the form of phosphorescence.But organic EL device of the prior art only has the short life of 150 hours, because the second-order transition temperature of CBP is very low, only 110 DEG C, and have the possibility of crystallization, adding users cost.
Therefore, prior art needs further to improve and develop.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a class electroluminescent organic material and apply in the devices, aiming to provide a kind of efficient electroluminescent organic material newly.
Technical scheme of the present invention is as follows:
A kind of containing quinoline derivatives, wherein, the general formula of molecular structure of described quinoline derivatives is:
Wherein, W, Z, X, Y are the one in carbon atom or nitrogen-atoms; Ar
1group to be carbonatoms be 6 ~ 14 aryl, Ar
2group to be carbonatoms be 12 ~ 30 aromatic heterocyclic radical.
Described contains quinoline derivatives, wherein, and described Ar
1group is the one in phenyl, xenyl, 2-naphthyl, 2-anthryl, N-phenyl-3-carbazyl or 2-phenanthryl.
Described contains quinoline derivatives, and wherein, the described quinoline derivatives that contains is:
in one.
A described preparation method containing quinoline derivatives, it comprises the steps:
Step S1: add 2-chloro-4-phenylquinoline analog derivative in reaction vessel, containing Ar
2the aminated compounds of group, potassium hydroxide and solvent:
Step S2: carry out degassed to reaction system, then add catalyzer;
Step S3: raise temperature of reaction to 140 DEG C-160 DEG C and reflux, fully reacting, obtains described containing quinoline derivatives.
Described preparation method, wherein, described solvent is oxine and dimethyl sulfoxide (DMSO).
Described preparation method, wherein, the chloro-4-phenylquinoline of the 2-in described step S1 analog derivative is prepared from by 2-chlorine-4-iodine base quinoline derivatives.
Described preparation method, wherein, the step preparing described 2-chloro-4-phenylquinoline analog derivative comprises:
Step N1: add 2-chlorine-4-iodine base quinoline derivatives in reaction vessel, containing Ar
1the boric acid that group replaces, salt of wormwood and solvent;
Step N2: carry out degassed to reaction system, then add catalyzer, raises temperature of reaction to 140 DEG C-160 DEG C and refluxes, fully reacting;
Step N3: obtain described 2-chloro-4-phenylquinoline analog derivative through extraction, washing, drying, column chromatography purification.
A kind of organic electroluminescent device, wherein, what comprise the first electrode, the second electrode and be placed between described first electrode, described second electrode is one or more containing quinoline derivatives layer.
A kind of containing the application of quinoline derivatives in organic electroluminescence device, wherein, the described quinoline derivatives that contains is used as phosphorescent red material of main part, fluorescent red material of main part, hole-injecting material or hole mobile material in described organic electroluminescence device.
A class electroluminescent organic material provided by the invention and applying in the devices, containing quinoline derivatives, there is high luminous efficiency, high luminous efficiency shows that this compound can be used as luminescent material or light emitting host material, be applied in organic electroluminescence device, its manufacturing cost is lower, extend the life-span of organic electroluminescence device, reduce the manufacturing cost of organic electroluminescence device.
Embodiment
The invention provides a class electroluminescent organic material and apply in the devices, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of containing quinoline derivatives, the general formula of molecular structure of wherein said quinoline derivatives is:
W, Z, X, Y are the one in carbon atom or nitrogen-atoms; Ar
1group to be carbonatoms be 6 ~ 14 aryl, Ar
2group to be carbonatoms be 12 ~ 30 aromatic heterocyclic radical.
And described Ar
1group is the one in phenyl, xenyl, 2-naphthyl, 2-anthryl, N-phenyl-3-carbazyl or 2-phenanthryl.
Further, described is one in table 1 in sequence number 1-46 containing quinoline derivatives.
Table 1
Present invention also offers a kind of described preparation method containing quinoline derivatives, it comprises the steps:
Step S1: add 2-chloro-4-phenylquinoline analog derivative in reaction vessel, containing Ar
2the aminated compounds of group, potassium hydroxide and solvent:
Step S2: carry out degassed to reaction system, then add catalyzer;
Step S3: raise temperature of reaction to 140 DEG C-160 DEG C and reflux, fully reacting, obtains described containing quinoline derivatives.Wherein, described solvent is oxine and dimethyl sulfoxide (DMSO).
Further, the 2-chloro-4-phenylquinoline analog derivative in described step S1 is prepared from by 2-chlorine-4-iodine base quinoline derivatives.Its step comprises:
Step N1: add 2-chlorine-4-iodine base quinoline derivatives in reaction vessel, containing Ar
1the boric acid that group replaces, salt of wormwood and solvent;
Step N2: carry out degassed to reaction system, then add catalyzer, raises temperature of reaction to 140 DEG C-160 DEG C and refluxes, fully reacting;
Step N3: obtain described 2-chloro-4-phenylquinoline analog derivative through extraction, washing, drying, column chromatography purification.
In order to further describe preparation method of the present invention, be described in detail for the quinoline derivatives that contains that sequence number is 9.
Prepare compound 9
By 2-chlorine-4-iodine quinazoline 50g (172.122mmol); phenylo boric acid 25.19g (206.54mmol), is dissolved in 1L toluene, and carries out degassed; add tetra-triphenylphosphine palladium 11.7g (10.15mmol) under nitrogen protection; salt of wormwood 10.52g (761.28mmol), distilled water 100mL, stirring and refluxing reacts 24 hours; distilled water is added under reaction terminates rear normal temperature; be extracted with ethyl acetate collected organic layer, with anhydrous magnesium sulfate drying, filter.Liquid is obtained after underpressure distillation, then column chromatography, draw white solid intermediate 2-chloro-4-phenylquinoline derivative 28.9g, productive rate is 70%.
Then by white solid intermediate 2-chloro-4-phenylquinoline analog derivative 5g (20.77mmol); carbazole 4.16g (24.92mmol); cupric iodide 0.79g (4.17mmol); potassium hydroxide 1.17g (2.86mmol); oxine 2.01g (13.91mmol); dimethyl sulfoxide (DMSO) (DMSO) 100mL, under nitrogen protection condition, under be warming up to 150 DEG C of stirrings.Under reaction end is cooled to normal temperature (25 DEG C) condition, add methyl alcohol, then the solid filtering generated, again the solid of filtration is added distilled water and methanol wash, use methylene dichloride and recrystallizing methanol again, draw sequence number be 9 containing quinoline derivatives 5.4g, productive rate is 70%.
As for the concrete preparation method of synthesis residue sequence number compound, and the usage quantity of each raw material, fully to react for standard, can determine as required, this is no longer going to repeat them.Only be the results are shown in table 2.
Table 2
Present invention also offers a kind of organic electroluminescent device, it is one or more containing quinoline derivatives layer that it comprises the first electrode, the second electrode and is placed between described first electrode, described second electrode.
And a kind of containing the application of quinoline derivatives in organic electroluminescence device, the quinoline derivatives that contains described in it is used as phosphorescent red material of main part, fluorescent red material of main part, hole-injecting material or hole mobile material in described organic electroluminescence device.
In order to more detailed description the present invention, below enumerate comparative sample and sample of the present invention carries out performance comparison.
Comparative sample
Chemical formula a is as light emitting host material below, chemical formula b is as dopant material below, the 2-TNATA (4 that chemical formula c represents, 4,4-tri-(N-naphthyl)-N-phenyl amino)-triphenylamine) be hole transporting material, make the organic electroluminescence device of structure below.
The TNATA (80nm) that chemical formula d is represented/α-NPD (30nm)/compound a+compound b (30nm)/Alq
3(30nm)/LiF (0.5nm)/Al (60nm).The EL evaporator making devices adopting DOV company to manufacture in the present embodiment and following examples, obtained contrast organic electroluminescence device.
The compound sample of sequence number 1-46 of the present invention
Adopted by compound a in comparative sample the cavitation compound of sequence number compound 1-46 of the present invention to replace, except other adopt be method ITO/DNTPD (80nm)/α-NPD (30nm)/[cavitation compound sequence 1 ~ 46 and doped compound]/b (8.0%) same in comparative sample] (25nm)/Alq
3(30nm) organic luminescent device of the structure of/LiF (0.5nm)/Al (60nm).
Measure 1: the luminescent properties of the compound sample of comparative sample and sequence number 1-46
The compound sample measuring comparative sample and sequence number 1-46 adopts KeithleySMU235, PR650 to evaluate driving voltage, luminosity, luminous efficiency, glow color.The compound sample of comparative sample and sequence number 1-46 is tested equally, and the results are shown in Table 3.
Table 3
Represented by table 3, the compound sample of comparative sample and sequence number 1-46, above-mentioned comparative sample shows glow color for red in 632-640nm wavelength region, and the described quinoline derivatives luminous efficiency that contains is significantly improved.
Measure: the life characteristic evaluation of the compound sample of comparative sample and sequence number 1-46
What adopt is the life-span determination device of the LTS-1004AC of ENC company, and take 3000nit as the time that benchmark determines that each life-span reaches 97%, result represents in table 4.
Table 4
| Sample No. | Host compound | Doped compound | Life-span [h] |
| Comparative sample | a | b | 72 |
| 1 | 1 | b | 180 |
| 2 | 2 | b | 153 |
| 3 | 3 | b | 197 |
| 4 | 4 | b | 105 |
| 5 | 5 | b | 120 |
| 6 | 6 | b | 98 |
| 7 | 7 | b | 90 |
| 8 | 8 | b | 188 |
| 9 | 9 | b | 138 |
| 10 | 10 | b | 172 |
| 11 | 11 | b | 122 |
| 12 | 12 | b | 130 |
| 13 | 13 | b | 195 |
| 14 | 14 | b | 186 |
| 15 | 15 | b | 174 |
| 16 | 16 | b | 160 |
| 17 | 17 | b | 91 |
| 18 | 18 | b | 164 |
| 19 | 19 | b | 116 |
| 20 | 20 | b | 117 |
| 21 | 21 | b | 90 |
| 22 | 22 | b | 100 |
| 23 | 23 | b | 107 |
| 24 | 24 | b | 101 |
| 25 | 25 | b | 96 |
| 26 | 26 | b | 199 |
| 27 | 27 | b | 101 |
| 28 | 28 | b | 98 |
| 29 | 29 | b | 152 |
| 30 | 30 | b | 112 |
| 31 | 31 | b | 114 |
| 32 | 32 | b | 102 |
| 33 | 33 | b | 97 |
| 34 | 34 | b | 104 |
| 35 | 35 | b | 108 |
| 36 | 36 | b | 103 |
| 37 | 37 | b | 94 |
| 38 | 38 | b | 98 |
| 39 | 39 | b | 181 |
| 40 | 40 | b | 116 |
| 41 | 41 | b | 100 |
| 42 | 42 | b | 92 |
| 43 | 43 | b | 93 |
| 44 | 44 | b | 116 |
| 45 | 45 | b | 97 |
| 46 | 46 | b | 116 |
Can determine according to table 4, comparative sample is compared with the compound sample of sequence number 1-46, and described quinoline derivatives luminescent lifetime is significantly improved.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (4)
1. containing a quinoline derivatives, it is characterized in that, the described quinoline derivatives that contains is:
in one.
2., as claimed in claim 1 containing a preparation method for quinoline derivatives, it comprises the steps:
Step S1: add 2-chloro-4-phenylquinoline analog derivative in reaction vessel, contain
the aminated compounds of group, potassium hydroxide and solvent:
Step S2: carry out degassed to reaction system, then add catalyzer;
Step S3: raise temperature of reaction to 140 DEG C-160 DEG C and reflux, fully reacting, obtains described containing quinoline derivatives;
Described solvent is oxine and dimethyl sulfoxide (DMSO);
2-in described step S1 chloro-4-phenylquinoline analog derivative is prepared from by 2-chlorine-4-iodine base quinoline derivatives;
The step preparing described 2-chloro-4-phenylquinoline analog derivative comprises:
Step N1: add 2-chlorine-4-iodine base quinoline derivatives in reaction vessel, contain
the boric acid that group replaces, salt of wormwood and solvent;
Step N2: carry out degassed to reaction system, then add catalyzer, raises temperature of reaction to 140 DEG C-160 DEG C and refluxes, fully reacting;
Step N3: obtain described 2-chloro-4-phenylquinoline analog derivative through extraction, washing, drying, column chromatography purification.
3. an organic electroluminescent device, is characterized in that, what comprise the first electrode, the second electrode and be placed between described first electrode, described second electrode is one or more containing quinoline derivatives layer;
The described quinoline derivatives that contains is:
in one or both.
4. one kind contains the application of quinoline derivatives in organic electroluminescence device, it is characterized in that, described is used as phosphorescent red material of main part, fluorescent red material of main part, hole-injecting material or hole mobile material containing quinoline derivatives in described organic electroluminescence device;
The described quinoline derivatives that contains is:
in one or both.
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| KR101513006B1 (en) | 2012-06-13 | 2015-04-17 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescence compounds and organic electroluminescence device containing the same |
| KR20150071624A (en) * | 2013-12-18 | 2015-06-26 | 롬엔드하스전자재료코리아유한회사 | Organic electroluminescent compound and organic electroluminescent device comprising the same |
| KR20150108330A (en) * | 2014-03-17 | 2015-09-25 | 롬엔드하스전자재료코리아유한회사 | Electron buffering material and organic electroluminescent device comprising the same |
| US9741941B2 (en) * | 2014-04-29 | 2017-08-22 | Universal Display Corporation | Organic electroluminescent materials and devices |
| KR102212972B1 (en) * | 2014-07-21 | 2021-02-05 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| WO2016198144A1 (en) | 2015-06-10 | 2016-12-15 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| US10971687B2 (en) * | 2017-12-14 | 2021-04-06 | Universal Display Corporation | Organic electroluminescent materials and devices |
| US11211568B2 (en) * | 2019-01-21 | 2021-12-28 | Luminescence Technology Corp. | Compound for organic electroluminescence device using the same |
| CN110143952A (en) * | 2019-06-17 | 2019-08-20 | 上海天马有机发光显示技术有限公司 | A kind of compound, display panel and display device |
| CN112110900A (en) * | 2020-09-09 | 2020-12-22 | 浙江华显光电科技有限公司 | Organic electroluminescent compound and organic light-emitting device using same |
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| CN102439004A (en) * | 2010-04-20 | 2012-05-02 | 出光兴产株式会社 | Bicarbazole derivative, material for organic electroluminescent element, and organic electroluminescent element using same |
| CN102625806A (en) * | 2009-07-31 | 2012-08-01 | 罗门哈斯电子材料韩国有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN103242299A (en) * | 2013-05-16 | 2013-08-14 | 吉林大学 | Quinazoline derivative and application thereof in organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102625806A (en) * | 2009-07-31 | 2012-08-01 | 罗门哈斯电子材料韩国有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN102439004A (en) * | 2010-04-20 | 2012-05-02 | 出光兴产株式会社 | Bicarbazole derivative, material for organic electroluminescent element, and organic electroluminescent element using same |
| CN103242299A (en) * | 2013-05-16 | 2013-08-14 | 吉林大学 | Quinazoline derivative and application thereof in organic electroluminescent device |
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