CN104403661A - Organic electroluminescent material and applications thereof - Google Patents
Organic electroluminescent material and applications thereof Download PDFInfo
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- CN104403661A CN104403661A CN201410625715.6A CN201410625715A CN104403661A CN 104403661 A CN104403661 A CN 104403661A CN 201410625715 A CN201410625715 A CN 201410625715A CN 104403661 A CN104403661 A CN 104403661A
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- naphthalene
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- 239000000463 material Substances 0.000 title abstract description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 24
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004305 biphenyl Substances 0.000 claims abstract description 12
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 12
- 150000002220 fluorenes Chemical class 0.000 claims description 14
- 239000011368 organic material Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- 238000005893 bromination reaction Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 45
- 238000005401 electroluminescence Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000007738 vacuum evaporation Methods 0.000 description 12
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000027756 respiratory electron transport chain Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241001269238 Data Species 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- -1 alcohol ester Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- BZTRTBHTECKHDX-UHFFFAOYSA-N Brc(cc1C(c2ccccc2-c2c3)(c2cc-2c3-c3ccnc4c3c-2ccn4)c2c3)ccc1-c2ccc3Br Chemical compound Brc(cc1C(c2ccccc2-c2c3)(c2cc-2c3-c3ccnc4c3c-2ccn4)c2c3)ccc1-c2ccc3Br BZTRTBHTECKHDX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HYCYKHYFIWHGEX-UHFFFAOYSA-N (2-phenylphenyl)boronic acid Chemical group OB(O)C1=CC=CC=C1C1=CC=CC=C1 HYCYKHYFIWHGEX-UHFFFAOYSA-N 0.000 description 1
- IAEUFBDMVKQCLU-UHFFFAOYSA-N (4-propan-2-ylphenyl)boronic acid Chemical compound CC(C)C1=CC=C(B(O)O)C=C1 IAEUFBDMVKQCLU-UHFFFAOYSA-N 0.000 description 1
- MNJYZNVROSZZQC-UHFFFAOYSA-N (4-tert-butylphenyl)boronic acid Chemical compound CC(C)(C)C1=CC=C(B(O)O)C=C1 MNJYZNVROSZZQC-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical class N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical group BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- SIADAGFXEHBPGG-UHFFFAOYSA-N 4-chloro-1,8-naphthyridine Chemical class C1=CC=C2C(Cl)=CC=NC2=N1 SIADAGFXEHBPGG-UHFFFAOYSA-N 0.000 description 1
- IWZYAPYZGBVTKJ-UHFFFAOYSA-N B(O)O.C1=CC=CC2=CC=CC=C12.CC1=C(C(=O)O)C=CC=C1C(=O)O Chemical class B(O)O.C1=CC=CC2=CC=CC=C12.CC1=C(C(=O)O)C=CC=C1C(=O)O IWZYAPYZGBVTKJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LGLORHOIWIGOJF-SMGVGDBXSA-N CC1(C)c2ccccc2C/C1=C\C(\c(cc1)cc(C(c2ccccc2-c2c3)(c2cc-2c3-c3ccnc4c3c-2ccn4)c2c3)c1-c2ccc3-c1ccc2-c3ccccc3C(C)(C)c2c1)=C/C Chemical compound CC1(C)c2ccccc2C/C1=C\C(\c(cc1)cc(C(c2ccccc2-c2c3)(c2cc-2c3-c3ccnc4c3c-2ccn4)c2c3)c1-c2ccc3-c1ccc2-c3ccccc3C(C)(C)c2c1)=C/C LGLORHOIWIGOJF-SMGVGDBXSA-N 0.000 description 1
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 240000003211 Corylus maxima Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- LEAUNHVLOCSTSS-UHFFFAOYSA-N c(cc1C(c2c3)(c4c5)c(cc(cc6)-c7cc(cccc8)c8cc7)c6-c4ccc5-c4cc5ccccc5cc4)ccc1-c2cc-1c3-c2ccnc3c2c-1ccn3 Chemical compound c(cc1C(c2c3)(c4c5)c(cc(cc6)-c7cc(cccc8)c8cc7)c6-c4ccc5-c4cc5ccccc5cc4)ccc1-c2cc-1c3-c2ccnc3c2c-1ccn3 LEAUNHVLOCSTSS-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic electroluminescent material and applications thereof. The structure of the organic electroluminescent material is represented by the formula (I), wherein the Ar1 represents a benzene, naphthalene, biphenyl, phenanthrene or fluorene group without any substitute, or a benzene, naphthalene, biphenyl, phenanthrene or fluorene group with a substitute; and the Ar2 represents a benzene, naphthalene, biphenyl, phenanthrene or fluorene group without any substitute, or a benzene, naphthalene, biphenyl, phenanthrene or fluorene group with a substitute. The organic micromolecular material with a parallel ring structure is synthesized through coupling reactions, bromination reactions, and cyclization reactions.
Description
Technical field
The present invention relates to a kind of electroluminescent organic material and application thereof, be specifically related to a kind of organic electroluminescent LED (OLED) material and application thereof.
Background technology
Organic electroluminescent diode (OLED) results from the eighties in last century, compared with traditional liquid crystal, OLED technique of display, there is luminous, wide viewing angle, fast response time, can the plurality of advantages such as Flexible Displays be realized, therefore be considered to likely replace traditional liquid crystal, become the main flow of technique of display of future generation.More than two decades comes, and along with the ongoing effort of production, teaching & research all circles, at present, has had the multiple commodity based on OLED technique of display to realize industrialization.
In order to realize full-color display, needing the display device unit of red, green, blue three kinds of primary colours at least respectively, comparing with red device with green device, at present, it is on the low side that blue-light device still also exists device efficiency, the deficiency that purity of color is poor.
The standard blue light of International Commission on Illumination's definition, CIE
x,ycoordinate is (0.15,0.08), and usual blue-light-emitting y value being less than 0.10 is defined as dark blue light at present, use the display unit that mazarine luminescent device makes, its display colour gamut is more broad, and color is more true to nature, therefore, exploitation mazarine luminescent material, has realistic meaning.
9,9'-spiral shell two fluorenes has three orthogonal space structure, can reduce molecular crystal trend, be conducive to obtaining stable amorphous organic film, but, 9,9'-not modified spiral shell two fluorenes, there is conjugate length partially short, the structure problem that fluorescence quantum efficiency is on the low side, therefore, 9,9'-spiral shell two fluorenes itself, and be not suitable as luminescent material use.
Summary of the invention
Technical problem to be solved by this invention is to provide one and has good luminescent properties, has electroluminescent organic material and the application thereof of certain carrier transport ability concurrently simultaneously.
The present invention, at the specific site of 9,9'-spiral shell two fluorenes, introduces [1,8] naphthyridines structural unit, this structural modification, is conducive to the carrier transport ability improving target molecule; Adopt the mode of also ring to connect, be conducive to the plane configuration keeping target molecule upper end portion, be conducive to the three orthogonal space structure keeping target molecule entirety; By carrying out suitable chemically modified to the fluorenes ring of 9,9'-spiral shell two fluorenes lower end, being conducive to regulating the spectrum color of target molecule, by above structural modification, a class performance can being obtained preferably, have carrier transmission performance, blue organic electroluminescent material concurrently.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of electroluminescent organic material, has the structure met shown in formula I:
Wherein, described Ar
1for not containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes, or, containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes;
Described Ar
2for not containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes, or, containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described Ar
1with described Ar
2identical or not identical.
Another technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of application of electroluminescent organic material:
Preparing in organic electroluminescent diode apparatus, having a functional layer at least, containing the electroluminescent organic material described in any one of claim 1 or 2, namely this material as blue emitting material, can be applied in field of organic electroluminescence.
The invention has the beneficial effects as follows:
The invention provides a class to have and the organic small molecule material of ring structure, and provide the preparation method of such material, such material has good luminescent properties, have certain carrier transport ability concurrently simultaneously, the organic electroluminescence device made using such material as blue emitting material, illustrate good usefulness, its feature is:
1., by linked reaction, bromo-reaction, the polystep reactions such as ring closure reaction, have synthesized a class and have had and the organic small molecule material of ring structure.
2. such material has good luminescent properties, has certain carrier transport ability concurrently simultaneously, and such material as blue emitting material, can be applied in field of organic electroluminescence.
3. using such material as emitting layer material, using TPBI as electron transport material, the organic electroluminescence device (embodiment 16-embodiment 20) of preparation, CIE
x,ycoordinate (0.15-0.17,0.07-0.10), be the good mazarine luminescent device of purity of color, device maximum current efficiency 1.4-2.2cd/A, device efficiency is better.
4. using such material as luminescent material, simultaneously as electron transport material, the organic electroluminescence device (embodiment 21-embodiment 22) of preparation, device CIE
x,ycoordinate (0.15-0.16,0.07-0.10), maximum current efficiency 0.42-0.61cd/A, such device architecture illustrates that target molecule has certain carrier transport ability.
01 ~ the C14 of Compound C shown in following formula, being the representative structure meeting the present invention's spirit and principle, should be appreciated that the concrete structure listing following compound, just in order to explain the present invention better, is not limitation of the present invention.
The preparation method of material described in the present invention is as follows:
First be the preparation of key intermediates, compound 6, reaction scheme is shown below:
Further with compound 6 for raw material, carry out linked reaction from different substrate respectively, obtain target compound, specific experiment process, refers to embodiment 7-embodiment 15 in embodiment.
The invention provides the organic small molecule material that a class has closed-loop structure, and provide the preparation method of such material, simultaneously, also will provide using such material as functional layer, be applied to the application example in organic electroluminescence device, such material can be used as blue emitting material, is applied in organic electroluminescence device.
Prepared organic electroluminescence device generally comprises the ITO Conducting Glass (anode), hole transmission layer (NPB), luminescent layer (electroluminescent organic material of the present invention), electron transfer layer (electroluminescent organic material of the present invention or TPBI), electron injecting layer (LiF) and the cathode layer (Al) that superpose successively.
The structural representation of prepared organic electroluminescence device is as shown in accompanying drawing 1 or accompanying drawing 2.All functions layer all adopts vacuum evaporation process to make, pressure <1.0X10
-3pa, the molecular structural formula of some organic compound used in device is shown below.
Accompanying drawing explanation
A wherein structural representation of the organic electroluminescence device of Fig. 1 prepared by the present invention;
Wherein another structural representation of the organic electroluminescence device of Fig. 2 prepared by the present invention;
In accompanying drawing, the list of parts representated by each label is as follows:
1, ITO Conducting Glass, 2, hole transmission layer, 3, luminescent layer, 4, electron transfer layer, 5, electron injecting layer, 6, cathode layer, 7, luminescent layer holds concurrently electron transfer layer.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Compound prepares embodiment:
The preparation of embodiment 1 compound 1
In 3L there-necked flask, add the bromo-5-of 4-chloro-[1,8] naphthyridines (126.9g, 0.52mol), adjacent biphenylboronic acids Knit-the-brows any alcohol ester (165g, 0.50mol), K
2cO
3(125g, 0.9mol), toluene (1200mL), deionized water (600mL), N
2protection, adds Pd (OAc)
2(4.5g, 0.02mol), Phosphine ligands 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-1,1 '-biphenyl (16.4g, 0.04mol), N
2under protection, be warming up to backflow, insulation reaction 48h, be down to room temperature, separatory, 500mL deionized water wash organic phase 1 time, collect organic phase, anhydrous Na
2sO
4drying, filters, and filtrate is quickly through the thick layer of silica gel of 10cm, and slough solvent, crude product take Virahol as solvent recrystallization, obtains yellow crystals 72.5g, yield 71.0%, MS (m/s): 204.1.
The preparation of embodiment 2 compound 2
In 2L there-necked flask, add compound 1 (71.5g, 0.35mol), oil of mirbane (1200mL), bromine (67.2g, 0.42mol), be warming up to interior temperature 145-150 DEG C, insulation reaction is about 8h, be down to room temperature, by in reaction solution slowly impouring 2500mL methyl alcohol, rapid stirring is about 1h, suction filtration, collect filter cake in 2L Erlenmeyer flask, add 1200g deionized water, about 45g S-WAT, stir 1h, suction filtration, collect filter cake in 2L Erlenmeyer flask, add methyl alcohol 600mL, stirring at room temperature 1h, suction filtration, collect filter cake, air-dry, obtain pale pink solid 75.8g, yield 76.5%, MS (m/s): 282.0.
The preparation of embodiment 3 compound 3
In 2L there-necked flask, add compound 2 (75.0g, 0.26mol), duplex boric acid Knit-the-brows any alcohol ester (76.2g, 0.30mol), Pd (PPh
3)
4(6.5g, 0.0056mol), potassium acetate (41.2g; 0.42mol); Isosorbide-5-Nitrae-dioxane (1100mL), under nitrogen protection; be warming up to interior temperature 102 DEG C; insulation reaction 9h, is down to room temperature, 300mL deionized water wash organic phase 1 time; separatory; collect organic phase, slough solvent, crude product crosses purification by silica gel column chromatography; eluent is sherwood oil: ethyl acetate=1:3; further use dehydrated alcohol recrystallization purifying, obtains compound 3, off-white color solid 67.2g; yield 78.3%, MS (m/s): 330.1.
The preparation of embodiment 4 compound 4
In 2L there-necked flask, add compound 4 (66.2g, 0.20mol), adjacent bromo-iodobenzene (113.2g, 0.4mol), Pd (PPh
3)
4(6.5g, 0.0056mol), K
2cO
3(110g, 0.8mol), toluene (800mL); deionized water (300mL), under nitrogen protection, is warming up to backflow; insulation reaction 18h, is down to room temperature, separatory; 200mL toluene aqueous phase extracted, merges organic phase, sloughs solvent; thick product take Virahol as solvent, and recrystallization purifying, obtains hazel-color solid 61.5g; yield 85.6%, MS (m/s): 358.0.
The preparation of embodiment 5 compound 5
In 2L there-necked flask, add compound 4 (60.9g, 0.17mol), THF (350mL), toluene (450mL), be cooled to-78 DEG C, slowly instill the hexane solution (76mL of n-Butyl Lithium, 2.5mol/L, 0.19mol), insulation reaction 2.5h,-78 DEG C, add solid 2 in batches, 7-dibromo fluorenone (64.2g, 0.19mol), insulation reaction 4h, reaction flask is moved into room temperature, naturally room temperature is warming up to, stir 1h, the hydrochloric acid reaction of instillation 300mL mass concentration 10%, stir 0.5h, separatory, collect organic phase, slough solvent, obtain compound 5, sticky oil thing 110g, the thick product of gained is no longer further purified, be directly used in next step reaction.
The preparation of embodiment 6 compound 6
In 2L there-necked flask, add compound 5 crude product 110g, glacial acetic acid 850g, be warming up to interior temperature about 100 DEG C, obtain the brown solution clarified, instill about 2.0g concentrated hydrochloric acid, after about 10min, solid is had to separate out, 100-105 DEG C, insulation reaction 5h, be down to room temperature, suction filtration, the drip washing of 200mL dehydrated alcohol, collect filter cake, add 1200g sym-trimethylbenzene, be warming up to interior temperature 160 DEG C, obtain filbert clear liquid, be down to room temperature, hazel-color solid is had to separate out, suction filtration, the drip washing of 300mL sherwood oil, air-dry, obtain compound 6, gross weight 61.2g, two-step reaction yield 60.6%, MS (m/s): 598.0.
The preparation of embodiment 7 Compound C 01
In 250mL there-necked flask, add compound 6 (4.2g, 7mmol), phenylo boric acid (1.95g, 16mmol), THF (60mL), deionized water (30mL), salt of wormwood (5.8g, 42mmol), Pd (PPh
3)
4(0.57g, 0.5mmol), N
2protection, be warming up to backflow, insulation reaction 18h, be down to room temperature, separatory, collect organic phase, anhydrous sodium sulfate drying, filter, collect filtrate, filtrate is quickly through the thick layer of silica gel of about 10cm, slough solvent, obtain 3.8g target compound crude product, collect above thick product, add 120mL orthodichlorobenzene, be warming up to interior temperature about 155 DEG C, obtain clear liquor, while hot quickly through the silicagel column that 10cm is thick, collected post liquid, naturally room temperature is down to, placement is spent the night, off-white color solid is had to separate out, suction filtration, air-dry, obtain target compound C01, off-white color solid 2.85g, use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 360 DEG C, obtain 2.2g target compound C01, yield 52.4%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
45h
26n
2, theoretical value 594.2096, test value 594.2099.
The preparation of embodiment 8 Compound C 04
With compound 6 and 4-isopropyl benzene boronic acid for raw material, prepare Compound C 04 according to method described in embodiment 7, yield 61.2%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
51h
38n
2, theoretical value 678.3035, test value 678.3039.
The preparation of embodiment 9 Compound C 05
With compound 6 and 4-tert-butylbenzeneboronic acid for raw material, prepare Compound C 05 according to method described in embodiment 7, yield 55.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
53h
42n
2, theoretical value 706.3348, test value 706.3346.
The preparation of embodiment 10 Compound C 06
With compound 6 and 1-naphthalene boronic acids for raw material, prepare Compound C 06 according to method described in embodiment 7, yield 63.2%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
53h
30n
2, theoretical value 694.2409, test value 694.2411.
The preparation of embodiment 11 Compound C 07
With compound 6 and 2-methyl isophthalic acid-naphthalene boronic acids for raw material, prepare Compound C 07 according to method described in embodiment 7, yield 59.6%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
55h
34n
2, theoretical value 722.2722, test value 722.2725.
The preparation of embodiment 12 Compound C 08
With compound 6 and 4-phenyl-1-naphthalene boronic acids for raw material, prepare Compound C 08 according to method described in embodiment 7, yield 49.8%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
65h
38n
2, theoretical value 846.3035, test value 846.3038.
The preparation of embodiment 13 Compound C 09
With compound 6 and 2-naphthalene boronic acids for raw material, prepare Compound C 06 according to method described in embodiment 7, yield 61.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
53h
30n
2, theoretical value 694.2409, test value 694.2413.
The preparation of embodiment 14 Compound C 12
With the luxuriant and rich with fragrance boric acid of compound 6 and 9-for raw material, prepare Compound C 12 according to method described in embodiment 7, yield 59.3%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
61h
34n
2, theoretical value 794.2722, test value 794.2724.
The preparation of embodiment 15 Compound C 13
With compound 6 and 9,9-dimethyl fluorene-2-boric acid for raw material, prepare Compound C 13 according to method described in embodiment 7, yield 56.9%.
High resolution mass spectrum, ESI source, positive ion mode, molecular formula C
63h
42n
2, theoretical value 826.3348, test value 826.3345.
Organic electroluminescence device embodiment:
The present invention chooses Compound C 05, Compound C 06, Compound C 07, Compound C 12 and Compound C 13 make first group of organic electroluminescence device, device architecture as shown in Figure 1, described device implementation process and result, just in order to explain the present invention better, not limitation of the present invention.By lower floor to upper strata, be followed successively by ITO Conducting Glass 1, hole transmission layer 2, luminescent layer 3, electron transfer layer 4, electron injecting layer 5 and cathode layer 6, wherein luminescent layer 3 is made up of electroluminescent organic material of the present invention.
The application of embodiment 16 Compound C 05 in organic electroluminescence device
The present embodiment prepares organic electroluminescence device one by the following method:
A) ITO (tin indium oxide) glass is cleaned: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) on anode ito glass, vacuum evaporation hole transmission layer (NPB) 2, thickness is 50nm;
C) on hole transmission layer (NPB) 2, vacuum evaporation luminescent layer (C05) 3, thickness is 30nm;
D) on luminescent layer 3, vacuum evaporation electron transfer layer (TPBI) 4, thickness is 30nm;
E) on electron transfer layer (TPBI) 4, vacuum evaporation electron injecting layer (LiF) 5, thickness is 1nm;
F) on electron injecting layer 5, vacuum evaporation cathode layer (Al) 6, thickness is 100nm.
The structure of device one is ITO/NPB (50nm)/Compound C 05 (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm), in vacuum evaporation process, and pressure <1.0X10
-3pa, device one open bright voltage, maximum current efficiency, the photooptical datas such as purity of color see below civilian table 1 (in embodiment 20).
The application of embodiment 17 Compound C 06 in organic electroluminescence device
Replace Compound C 05 as luminescent layer using Compound C 06, according to method described in embodiment 16, be manufactured with organic electroluminescence devices two, the structure of device two is ITO/NPB (50nm)/Compound C 06 (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm), device two open bright voltage, maximum current efficiency, the photooptical datas such as purity of color see below civilian table 1.
The application one of embodiment 18 Compound C 07 in organic electroluminescence device
Using Compound C 07 as luminescent layer, according to method described in embodiment 16, be manufactured with organic electroluminescence devices three, the structure of device three is ITO/NPB (50nm)/Compound C 07 (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm), device three open bright voltage, maximum current efficiency, the photooptical datas such as purity of color, list in hereinafter in table 1.
The application of embodiment 19 Compound C 12 in organic electroluminescence device
Using Compound C 12 as luminescent layer, according to method described in embodiment 16, be manufactured with organic electroluminescence devices four, the structure of device four is ITO/NPB (50nm)/Compound C 12 (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm), device four open bright voltage, maximum current efficiency, the photooptical datas such as purity of color see below civilian table 1.
The application of embodiment 20 Compound C 13 in organic electroluminescence device
Using Compound C 13 as luminescent layer, according to method described in embodiment 16, be manufactured with organic electroluminescence devices five, the structure of device five is ITO/NPB (50nm)/Compound C 13 (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm), device five open bright voltage, maximum current efficiency, the photooptical datas such as purity of color are in table 1.
Table 1 device one to device five photooptical data table
Using material provided by the invention as luminescent material, the organic electroluminescence device made using TPBI as electron transport material, illustrates good usefulness, device CIE
x,ycoordinate (0.15-0.17,0.07-0.10), be the mazarine luminescent device that purity of color is splendid, maximum current efficiency 1.4-2.2cd/A, efficiency is better.
The present invention chooses Compound C 07 and Compound C 12 makes second group of organic electroluminescence device, and device architecture as shown in Figure 2, should be appreciated that device implementation process and result, just in order to explain the present invention better, and not limitation of the present invention.By lower floor to upper strata, be followed successively by ITO Conducting Glass 1, hole transmission layer 2, luminescent layer hold concurrently electron transfer layer 7, electron injecting layer 5 and cathode layer 6, wherein luminescent layer electron transfer layer 7 of holding concurrently relates to this case material.
The application two of embodiment 21 Compound C 07 in organic electroluminescence device
The present embodiment prepares organic electroluminescence device six by the following method:
A) ITO (tin indium oxide) glass is cleaned: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) on anode ito glass, vacuum evaporation hole transmission layer (NPB) 1, thickness is 50nm;
C) on hole transmission layer (NPB) 1, vacuum evaporation is simultaneously as luminescent layer and electron transfer layer (C07) 7, and thickness is 60nm;
D) on compound (C07) 7, vacuum evaporation electron injecting layer (LiF) 5, thickness is 1nm;
E) on electron injecting layer 5, vacuum evaporation cathode layer (Al) 6, thickness is 100nm.
The structure of device six is ITO/NPB (50nm)/Compound C 07 (60nm)/LiF (1nm)/Al (100nm), in vacuum evaporation process, and pressure <1.0X10
-3pa, device six open bright voltage, maximum current efficiency, the photooptical datas such as purity of color see below civilian table 2.
The application two of embodiment 22 Compound C 12 in organic electroluminescence device
Using Compound C 12 as luminescent layer and electron transfer layer, according to method described in embodiment 21, be manufactured with organic electroluminescence devices seven, the structure of device seven is ITO/NPB (50nm)/Compound C 12 (60nm)/LiF (1nm)/Al (100nm), device seven open bright voltage, maximum current efficiency, the photooptical datas such as purity of color are in table 2.
Table 2 device six to device seven photooptical data table
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. an electroluminescent organic material, is characterized in that, described electroluminescent organic material has the structure met shown in formula I:
Wherein, described Ar
1for not containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes, or, containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes;
Described Ar
2for not containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes, or, containing any one in substituent benzene, naphthalene, biphenyl, phenanthrene or fluorenes.
2. electroluminescent organic material according to claim 1, is characterized in that, described Ar
1with described Ar
2identical or not identical.
3. an application for electroluminescent organic material, is characterized in that, is preparing in organic electroluminescent diode apparatus, has a functional layer at least, containing the electroluminescent organic material described in claim 1 or 2.
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| KR20130122602A (en) * | 2013-10-24 | 2013-11-07 | 주식회사 엘지화학 | New compounds and organic electronic device using the same |
| CN103718316A (en) * | 2011-07-29 | 2014-04-09 | 默克专利有限公司 | Compounds for electronic devices |
| WO2014094963A1 (en) * | 2012-12-21 | 2014-06-26 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
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| US20110198989A1 (en) * | 2010-02-15 | 2011-08-18 | Canon Kabushiki Kaisha | Novel organic compound and organic light-emitting element using the same |
| CN103718316A (en) * | 2011-07-29 | 2014-04-09 | 默克专利有限公司 | Compounds for electronic devices |
| WO2014094963A1 (en) * | 2012-12-21 | 2014-06-26 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| KR20130122602A (en) * | 2013-10-24 | 2013-11-07 | 주식회사 엘지화학 | New compounds and organic electronic device using the same |
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