CN1152942C - Molecular twisty type electroluminescence material containing current carrier transmission functional group and its application - Google Patents
Molecular twisty type electroluminescence material containing current carrier transmission functional group and its application Download PDFInfo
- Publication number
- CN1152942C CN1152942C CNB001162128A CN00116212A CN1152942C CN 1152942 C CN1152942 C CN 1152942C CN B001162128 A CNB001162128 A CN B001162128A CN 00116212 A CN00116212 A CN 00116212A CN 1152942 C CN1152942 C CN 1152942C
- Authority
- CN
- China
- Prior art keywords
- electroluminescent
- molecular
- functional group
- carbazole
- application
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 32
- 125000000524 functional group Chemical group 0.000 title claims abstract description 7
- 230000005540 biological transmission Effects 0.000 title description 2
- 238000005401 electroluminescence Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 22
- -1 amino, dimethylamino Chemical group 0.000 claims description 4
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000005936 piperidyl group Chemical group 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 3
- 230000021615 conjugation Effects 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000547 conjugated polymer Polymers 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 21
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 14
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- OXEUETBFKVCRNP-UHFFFAOYSA-N 9-ethyl-3-carbazolamine Chemical compound NC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 OXEUETBFKVCRNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910017073 AlLi Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GRXUCZIQNMYNOH-UHFFFAOYSA-N 9-benzylcarbazol-3-amine Chemical compound C12=CC=CC=C2C2=CC(N)=CC=C2N1CC1=CC=CC=C1 GRXUCZIQNMYNOH-UHFFFAOYSA-N 0.000 description 2
- AAJWNQNJILHMKA-UHFFFAOYSA-N 9-hexylcarbazol-3-amine Chemical compound NC1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 AAJWNQNJILHMKA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001716 carbazoles Chemical group 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical group C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Landscapes
- Indole Compounds (AREA)
Abstract
本发明公开了一种含载流子传输功能团的分子扭曲型电致发光材料及其在电致发光器件中的应用。该材料含有1，8-萘酰亚胺和咔唑功能团。这种发光材料可保证载流子的注入、复合到激子的产生都发生在分子内，简化器件的制作工艺。同时能避免共轭聚合物发光材料经常由于共轭离域度的变化而引起发光色度变化的缺陷。该发光材料应用于电致发光器件时，最大发光波长为518nm，呈黄绿光，在驱动电压20V下最大光亮度为4500cd/m2。The invention discloses a molecular twisted electroluminescent material containing carrier transporting functional groups and its application in electroluminescent devices. The material contains 1,8-naphthoimide and carbazole functional groups. This light-emitting material can ensure that the injection of carriers, recombination and generation of excitons all occur in the molecule, simplifying the manufacturing process of the device. At the same time, it can avoid the defect that the conjugated polymer luminescent material often causes the change of luminous chromaticity due to the change of the conjugation delocalization degree. When the luminescent material is applied to an electroluminescent device, the maximum luminous wavelength is 518nm, showing yellow-green light, and the maximum luminance is 4500cd/m 2 at a driving voltage of 20V.
Description
The invention belongs to field of fine chemical, relate to the electroluminescent material that a class contains the carrier transport functional group, relate in particular to and a kind ofly contain 1, the electroluminescent material and the application thereof of 8-naphthalimide and carbazole functional group.
In recent years, world market every year of flat pannel display, the rate of increase with 20% to 30% rose, and will rise to 200 to 40,000,000,000 dollars when expecting 2000.Present liquid-crystal display (LCD) accounts for 86% of whole flat pannel display market, becomes the main flow of flat pannel display.Compare with liquid-crystal display, the most competitive technology of new generation is that the organic thin film electroluminescent that occurs the end of the eighties shows, it has overcome the shortcoming of LCD fully, have low voltage direct drive, active illuminating, the visual angle is big, response speed is fast and low cost and other advantages, thereby it becomes the luminescence technology of new generation that various countries competitively invest and develop in luminous demonstration field.We can say, nearly all in the world famous relevant major company all drops into a large amount of man power and materials, joins in this competition that becomes a flash point day by day, so that capture market, and estimate that big area, the luminous demonstration of the organic film that can curl were expected to be used for flat panel TV in 2007.
The efficient of improving electroluminescent device must be optimized following three factors: the injection speed in (1) balance electronic and hole; (2) current carrier is compounded to form singlet exciton; (3) attenuation.
At present, the multilayer organic electroluminescence device that contains carrier blocking layers in succession the someone report.Yet along with the increase of the device number of plies, will cause layer with layer complexity effect such as interface, microcavity, can increase the manufacture difficulty of device simultaneously.For avoiding these shortcomings, constantly the someone reports adulterated individual layer electroluminescent device, and maximum external quantum efficiency can reach 1%.But this doping meeting causes device lifetime on the low side because of the separation of phase, low morphological stability etc.Chinese patent, application number 00111494.8 discloses electroluminescent block polymers containing more function groups, has obtained effect preferably in actual applications, but the leeway of further raising is still arranged.
Along with science and technology development, people are provided by the electroluminescent material that can provide performance more superior.
One of purpose of the present invention is to provide a kind of balance and novel molecular distortion type electroluminescent material that contains the carrier transport more function group of compound that has good anti-crystallization, high morphological stability and can keep electric charge carrier effectively;
Two of purpose of the present invention is to disclose the application of above-mentioned luminescent material in electroluminescent device.
Design of the present invention is such:
The contriver is on the basis of big quantity research, based on 1, the 8-naphthalimide is a kind of luminescent material (its electron affinity is about 3.1eV) of high performance electronic mode transmission, with carbazole (hole transport functional group, the energy level of its HOMO track is 5.80eV) with 1, the 8-naphthalimide connects by the covalent linkage key.Owing to exist 1 between the functional group, the repulsion drag effect of the carbonyl of 8-naphthalimide, carbazole functional group and 1,8-naphthalimide functional group is not located in one plane, molecular distortion has taken place, and this molecular distortion characteristic can further confirm by its absorption spectrum.Just look like to be corresponding 1, the absorption of 8-naphthalimide and carbazole mixes and is formed by stacking, do not change original 1, the conjugation delocalization degree of 8-naphthalimide, promptly do not change original 1, the electroluminescent wavelength of 8-naphthalimide.This novel molecular distortion type electroluminescent material that contains the carrier transport more function group can guarantee that the injection of current carrier, the generation that is compound to exciton all occur in intramolecularly, make the device single-layered, overcome heterogeneous, the layer and influences such as bed interface and microcavity effect, can make whole organic layer entirely lighting, simplify the manufacture craft of device.Can avoid simultaneously conjugated polymer luminescent material often owing to the variation of conjugation delocalization degree causes the defective that luminescent chromaticity changes.Such novel molecular distortion type electroluminescent material that contains the carrier transport more function group can be used as the individual layer or the double-deck electroluminescent material of high-quantum efficiency.
According to above-mentioned design, the invention provides the luminescent material that a class has one of following general structure:
Wherein:
R is respectively C
2H
5, C
4H
9, C
6H
13, C
6H
5CH
2, C
8H
17, C
10H
21, C
16H
33Or C
18H
37In a kind of;
X is respectively a kind of in amino, dimethylamino, diethylin, piperidyl or the piperazinyl.
Above-claimed cpd can adopt following method to synthesize:
1. at first synthesize 1 of replacement, 8-naphthalene acid anhydride and carbazole compound:
Said replacement 1,8-naphthalene acid anhydride is the compound with following general structure:
Wherein: X as mentioned above.
The synthetic method of this compound is as follows:
With 4-bromo-1, the secondary amine of 8-naphthalene acid anhydride, replacement and organic solvent (ethylene glycol monomethyl ether or N, dinethylformamide or N-Methyl pyrrolidone) are raw material, with CuSO
45H
2O or CuCl are catalyzer, and back flow reaction 2～8 hours is poured into and separated out solid in the frozen water, filter and collect 1 of replacement, 8-naphthalene acid anhydride.4-bromo-1, the secondary amine of 8-naphthalene acid anhydride, replacement and the ratio of organic solvent are:
4-bromo-1,8-naphthalene acid anhydride: the secondary amine of replacement: organic solvent
＝1∶(1.1～4.0)∶(10～30)。
4-bromo-1,8-naphthalene acid anhydride is the commercial reagent.
Said substituted carbazole unit is the compound of following general structure:
The synthetic method of this series compound can adopt document (S.F.Zhang, et al., Dyes ﹠amp; Pigments, 1995,27 (4), 287) prior art of being reported is synthesized.
1. molecular distortion type electroluminescent material compound synthetic that contains the carrier transport more function group
With 1 of replacement, the carbazole of 8-naphthalene acid anhydride, replacement and ethylene glycol monomethyl ether are that raw material carries out amidation, and back flow reaction 4～20 hours is poured into and separated out solid in the frozen water, filter and collect product, are target product.1 of replacement, the carbazole of 8-naphthalene acid anhydride, replacement and the ratio of ethylene glycol monomethyl ether are:
1 of replacement, 8-naphthalene acid anhydride: the carbazole of replacement: ethylene glycol monomethyl ether
＝1∶(1.0～3.0)∶(20～30)。
The molecular distortion type compound of institute's synthetic carrier transport more function group can be used to prepare electroluminescent device.
Fig. 1 is the structural representation of individual layer electroluminescent device.
Fig. 2 is the structural representation of double-deck electroluminescent device.
Wherein:
1-glass lined bottom
2-indium tin oxide layer (ITO)
The 3-carrier blocking layers
The 4-luminescent layer
5-metal film electrode layer
When luminescent material of the present invention was applied to electroluminescent device, maximum emission wavelength was 518nm, is yellow green light, was 1, and the feature of 8-naphthalimide functional group is luminous, and maximum luminance is 4500cd/m under driving voltage 20V
2
Further illustrate the present invention below in conjunction with example, monomer 3-amino-N-substituted carbazole and 3 wherein, but synthetic reference (S.F.Zhang, et al., the Dyes ﹠amp of 6-diamino-N-substituted carbazole; Pigments, 1995,27 (4), 287), but example does not limit protection scope of the present invention.
Embodiment 1
The molecular distortion type compound N ACz-1's of carrier transport more function group is synthetic:
In the 50ml there-necked flask; add 0.28g N-piperidines-1; 8-naphthalene acid anhydride (0.99mmol), 0.25g 3-amino-N-ethyl carbazole (1.19mol) and 10ml ethylene glycol monomethyl ether; reflux 12h under the argon shield; filter, filter cake dehydrated alcohol recrystallization gets solid 0.24g; productive rate 53%, m.p.＞270 ℃.IR(KBr)：3030，2930，2910，1700，1650，1585，1490，1450，1360，1340，1230，800，780，760，730em
-1.
1H-NMR(DMSO)：1.36(t，J＝7.0Hz，3H，-CH
2CH
3)，1.64(t，2H，piperidinering)，1.84(m，4H，piperidine?ring)，3.23(m，4H，piperidine?ring)，4.50(q，J＝7.0Hz，2H，-CH
2CH
3)，7.20(t，J＝7.4Hz，J＝7.5Hz，1H)，7.36(d，J＝8.2Hz，1H)，7.39(d×d，J＝8.5Hz，J＝1.7Hz，1H)，7.48(t，J＝7.3Hz，J＝8.2Hz，1H)，7.66(d，J＝8.2Hz，1H)，7.70(d，J＝8.5Hz，1H)，7.85(t，J＝8.2Hz，J＝8.5Hz，1H)，8.10(d，J＝2.0Hz，1H)，8.12(d，J＝7.1Hz，1H)，8.42(d，J＝7.9Hz，1H)，8.47(d，J＝8.2Hz，1H)，8.50(d，J＝8.3Hz，1H).MS(EI?70ev)m/e：474(13.399％)[M
++1]，473(32.088％)[M
+]，263(10.204％)，180(5.591％).Found：C78.03％，H?5.43％，N?8.94％.Calcd.：C?78.63％，H?5.75％，N?8.87％.
The molecular distortion type compound N ACz-2's of carrier transport more function group is synthetic:
With the 3-amino-N-ethyl carbazole among 3-amino-N-hexyl carbazole replacement embodiment 1, other is identical with embodiment 1, and the result is as follows:
m.p.244-246℃.IR(KBr)：3030，2930，2900，1700，1650，1585，1490，1450，1360，1340，1230，800，780，750，730cm
-1.
1H-NMR(CDCl
3)：0.89(t，J＝7.0Hz，3H，CH
3-)，1.35(m，6H，-(CH
2)
3-)，1.75(t，2H，piperidine?ring)，1.92(m，4H，piperidinering)，3.28(m，4H，piperidine?ring)，4.33(t，J＝7.2Hz，2H，NCH
2CH
2-)，7.21(t，J＝7.6Hz，J＝5.9Hz，1H)，7.24(d，J＝10.45Hz，1H)，7.37(d×d，J＝8.5Hz，J＝2.0Hz，1H)，7.42(d，1H)，7.46(t，1H)，7.52(d，J＝8.6Hz，1H)，7.72(d，J＝7.40Hz，1H)，8.03(m，2H)，8.46(d，J＝8.4Hz，1H)，8.59(d，J＝8.0Hz，1H)，8.65(d，J＝7.2Hz，1H).MS(EI?70ev)m/e：529(47.733％)[M
+]，458(71.099％)[M
+-C
5H
11]，263(34.910％)，179(41.252％).43(85.257％)[C
3H
7 +]，41(100％).Found：C?79.01％，?H?6.47％，N?8.12％.Calcd.：C79.38％，H?6.66％，N?7.93％.
The molecular distortion type compound N ACz-3's of carrier transport more function group is synthetic:
With the 3-amino-N-ethyl carbazole among 3-amino-N-benzyl carbazole replacement embodiment 1, other is identical with embodiment 1, and the result is as follows:
m.p.＞270℃.IR(KBr)：3030，2960，2630，2900，1700，1650，1580，1490，1460，1380，1350，1220，800，780，720cm
-1.
1H-NMR(CDCl
3)：1.75(t，J＝6.0Hz，2H，piperidine?ring)，1.92(m，4H，piperidine?ring)，3.28(t，4H，piperidine?ring)，5.56(s，2H，-NCH
2Ph)，7.26(m，7h)，7.33(d×d，J＝8.5Hz，J＝2.0Hz，1H)，7.42(m，2H)，7.50(d，J＝8.5Hz，1H)，7.72(q，J＝8.4Hz，J＝8.4Hz，1H)，8.01(d，J＝8.1Hz，1H)，8.06(d，J＝1.9Hz，1H)，8.46(d×d，J＝8.5Hz，J＝1.1Hz，1H)，8.57(d，J＝8.0Hz，1H)，8.64(d×d，J＝7.2Hz，J＝1.1Hz，1H).MS(EI?70ev)m/e：536(8.693％)[M
++1]，535(19.2％)[M
+]，263(29.7％)，179(9.459％)，91(100％)[C
6H
5CH
2 +].Found：C?80.18％，H?5.49％，N?7.89％.Calcd.：C80.72％，H?5.45％，N?7.84％.
The molecular distortion type compound N ACz-4's of carrier transport more function group is synthetic:
In the there-necked flask of 50ml, add 0.5g N; N-dimethyl-1; 8-naphthalene acid anhydride (2.07mmol), 0.53g 3-amino-N-ethyl carbazole (2.5mol) and 17ml ethylene glycol monomethyl ether; reflux 12h under argon shield; filter, filter cake dehydrated alcohol recrystallization gets solid 0.37g; productive rate 42%, m.p.＞270 ℃.IR(KBr)：3030，2980，2960，2900，1690，1650，1580，1490，1360，1240，1180，1140，780，740cm
-1.
1H-NMR(CDCl
3)：1.48(t，J＝7.2Hz，3H，-CH
3CH
2N-)，3.15(s，6H，-N(CH
3)
2)，4.42(q，J＝7.2Hz，2h，CH
3CH
2N-)，7.17(d，J＝8.2Hz，1H)，7.22(t×d，J＝8.3Hz，J＝7.4Hz，J＝1.0Hz，1H)，7.38(d×d，J＝8.5Hz，J＝2.0Hz，1H)，7.41(d，J＝8.2Hz，1H)，7.48(t×d，J＝8.2Hz，J＝7.0Hz，J＝1.0Hz，1H)，7.56(d，J＝8.5Hz，1H)，7.72(q，J＝8.5Hz，J＝8.5Hz，1H)，8.03(d，J＝8.1Hz，1H，H)，8.05(s，1H)，8.51(d×d，J＝8.5Hz，J＝1.1Hz，1H)，8.56(d，J＝8.2Hz，1H)，8.65(d×d，J＝7.2Hz，J＝1.1Hz，1H).MS(EI?70ev)m/e：434(21.934％)[M
++1]，433(55.976％)[M
+]，419(10.431％)[M
+-C
2H
5]，418(23.084％)，223(34.880％)，208(13.375％)，180(15.266％).Found：C?77.63％，H?5.94％，N?9.38％.Calcd.：C77.58％，H?5.35％，N?9.69％.
The molecular distortion type compound N ACz-5's of carrier transport more function group is synthetic:
With the 3-amino-N-ethyl carbazole among 3-amino-N-hexyl carbazole replacement embodiment 4, the result is as follows:
m.p.＞270℃.IR(KBr)：3030，2960，2930，2900，1695，1650，1580，1490，1460，1360，780，750，730cm
-1.
1H-NMR(CDCl
3)：0.839(t，J＝7.0Hz，3H，-CH
3)，1.34(m，6H，-(CH
2)
3-)，1.91(t，2H，-NCH
2CH
2-)，3.15(s，6H，-N(CH
3)
2)，4.33(t，J＝7.2Hz，2H，-NCH
2-)，7.16(d，J＝8.2Hz，1H)，7.21(t，J＝7.3Hz，J＝7.4Hz，1H)，7.37(d×d，J＝8.5Hz，J＝1.0Hz，1H)，7.42(d，J＝8.2Hz，1H)，7.47(t，J＝7.7Hz，J＝7.3Hz，1H)，7.54(d，J＝8.5Hz，1H)，7.71(t，J＝7.8Hz，J＝7.9Hz，1H)，8.02(d，J＝8.0Hz，1H)，8.04(d，J＝1.7Hz，1H)，8.50(d，J＝8.4Hz，1H)，8.55(d，J＝8.2Hz，1H)，8.65(d，J＝7.1Hz，1H).MS(EI?70ev)m/e：490(100％)[M
++1]，419(67.613％)[M
+-C
5H
11]，223(11.464％).Found：C?78.69％，H?6.70％，N?8.14％.Calcd.：C?78.50％，H?6.38％，N?8.58％.
Embodiment 6
The molecular distortion type compound N ACz-6's of carrier transport more function group is synthetic:
With the 3-amino-N-ethyl carbazole among 3-amino-N-benzyl carbazole replacement embodiment 4, the result is as follows:
m.p.＞270℃.IR(KBr)：3030，2960，2940，2900，1695，1650，1580，1490，1460，1360，780，750，730cm
-1.
1H-NMR(DMSO)：3.14(s，6H，-N(CH
3)
2)，5.75(s，2H，-CH
2Ar)，7.27(m，7H)，7.37(d×d，J＝8.6Hz，J＝2.0Hz，1H)，7.49(t×d，J＝7.3Hz，J＝1.1Hz，1H)，7.72(d，J＝8.41Hz，1H)，7.72(d，J＝8.41Hz，1H)，7.75(d，8.7Hz，1H)，7.81(q，J＝8.5Hz，J＝8.5Hz，1H)，8.15(d，J＝2.0Hz，1H)，8.17(d，J＝7.9Hz)，8.39(d，J＝8.3Hz，1H)，8.50(d×d，J＝7.2Hz，J＝1.0Hz，1H)，8.79(d×d，J＝8.5Hz，J＝1.0Hz，1H)，8.50(d×d，J＝7.2Hz，J＝1.0Hz，1H)，8.79(d×d，J＝8.5Hz，J＝1.0Hz，1H).MS(EI?70ev)m/e：494(69.857％)[M
+-1]，223(74.880％)，91(100％)[C
6H
5CH
2 +].Found：C?79.52％，H?5.38％，N?8.59％.Calcd.：C?79.98％，H?5.08％，N?8.48％.
Embodiment 7
The molecular distortion type compound N ACz-7's of carrier transport more function group is synthetic:
In the 50ml there-necked flask; add 0.26g 3; 6-diamino-N-benzyl carbazole (0.90mmol), 0.50g N, N-piperidyl-1,8-naphthalene acid anhydride (1.8mmol) and 17ml ethylene glycol monomethyl ether; argon shield is reaction 15h down; filter, filter cake spent glycol monomethyl ether recrystallization gets the 0.41g product; productive rate 62%, m.p＞270 ℃.
1H-NMR(DMSO)：1.66(t，4H)，1.83(m，8H)，3.23(t，8H)，5.80(s，2H)，7.29(m，1H)，7.34(d×d，4H)，7.36(s，1H)，7.45(d×d，J＝8.96Hz，J＝1.93Hz，2H)，7，82(m，4H)，8.12(d，J＝1.93Hz，2H)，8.40(d，J＝8.16Hz，2H)，8.46(d×d，J＝7.31Hz，J＝8.56Hz，4H).
Embodiment 8
The molecular distortion type compound N ACz-8's of carrier transport more function group is synthetic:
In the 50ml there-necked flask; add 0.30g 3; 6-diamino-N-benzyl carbazole (1.1mmol), 0.50gN, N-dimethylamino-1,8-naphthalene acid anhydride (2.1mmol) and 17ml ethylene glycol monomethyl ether; argon shield was reacted 15 hours down; filter, filter cake spent glycol monomethyl ether recrystallization gets the 0.33g product; productive rate 47%, m.p.＞270 ℃.
1H-NMR(DMSO)：3.12(s，12H)，5.81(s，2H)，8.57(d，J＝8.52Hz，2H)，8.49(d，J＝7.23Hz，2H)，8.38(d，J＝8.28Hz，2H)，8.13(d，J＝1.84Hz，2H)，7.81(m，4H)，7.42(d×d，J＝8.62Hz，J＝1.84Hz，2H)，δ＝7.27(m，3H)，7.38(s，2H)，7.36(d×d，2H)。
Embodiment 9
With the molecular distortion type compound N ACz-1 of carrier transport more function group as electroluminescent material, preparation electroluminescent device as shown in Figure 1, the material and the structural parameter of each layer are as follows: glass substrate //ITO//CuPc (10nm)/TPD (10nm)/NACz-1 (30nm) //LiF (7nm)/AlLi;
The element manufacturing program is as follows: matrix adopts the ito glass of ultrasonic cleansing, and its resistance is 20 Ω/, the negative electrode (0.28cm of device
2) and organic thin film layer be to adopt vacuum vapour deposition coating (vacuum tightness is 1 * 10
-7Torr), wherein TPD is N, N '-triphenyl diamines, and CuPc is a copper phthalocyanine, plays the hole transport effect.The thickness of device is measured with step instrument (Tenco Alpha-step 500), and the electroluminescent spectrogram is to measure with PTI QM1 luminoscope.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak was 518nm, and being yellow green light is 1 of NACz-1, and the feature of 8-naphthalimide functional group is luminous, and luminosity is very high, reaches 4500cd/m
2, luminous efficiency is 0.91lm/W, current density is 400mA/cm
2Device through 48 hours continuously luminous after, luminosity still can maintain 100cd/m
2More than.
Embodiment 10
With the molecular distortion type compound N ACz-1 of carrier transport more function group as electroluminescent material, preparation electroluminescent device as shown in Figure 2, the material and the structural parameter of each layer are as follows: glass substrate //ITO//NACz-1 (83nm) //LiF (7nm)/AlLi;
Element manufacturing program and test similar embodiment 9.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak was 522nm, is yellow green light, reaches 3500cd/m
2, luminous efficiency is 0.85lm/W, current density is 250mA/cm
2Device through 48 hours continuously luminous after, luminosity still can maintain 100cd/m
2More than.
Embodiment 11
With the molecular distortion type compound N ACz-4 of carrier transport more function group as electroluminescent material, preparation electroluminescent device as shown in Figure 2, the material and the structural parameter of each layer are as follows:
Glass substrate //ITO//NACz-4 (110nm) //LiF (7nm)/AlLi;
Element manufacturing program and test similar embodiment 9.When driving voltage was 14V, the maximum emission wavelength in its electroluminescent peak was 520nm, is yellow green light, reaches 1200cd/m
2, luminous efficiency is 0.25lm/W, current density is 120mA/cm
2Device through 48 hours continuously luminous after, luminosity still can maintain 100cd/m
2More than.
Embodiment 12
With the molecular distortion type compound N ACz-7 of carrier transport more function group as electroluminescent material, preparation electroluminescent device as shown in Figure 2, the material and the structural parameter of each layer are as follows:
Glass substrate //ITO//NACz-7 (100nm) //LiF (7nm)/AlLi;
Element manufacturing program and test similar embodiment 9.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak was 522nm, is yellow green light, reaches 4800cd/m
2, luminous efficiency is 0.85lm/W, current density is 400mA/cm
2Device through 48 hours continuously luminous after, luminosity still can maintain 100cd/m
2More than.
Claims (2)
1. a class contains the molecular distortion type electroluminescent material of carrier transport functional group, it is characterized in that, be the compound that a class has one of following general structure:
Wherein:
R is respectively C
2H
5, C
4H
9, C
6H
13, C
6H
5CH
2, C
8H
17, C
10H
21, C
16H
33Or C
18H
37In a kind of;
X is respectively a kind of in amino, dimethylamino, diethylin, piperidyl or the piperazinyl.
2. the application of material as claimed in claim 1 is characterized in that can be used as the luminescent material of luminescent layer in the electroluminescent device (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001162128A CN1152942C (en) | 2000-05-30 | 2000-05-30 | Molecular twisty type electroluminescence material containing current carrier transmission functional group and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001162128A CN1152942C (en) | 2000-05-30 | 2000-05-30 | Molecular twisty type electroluminescence material containing current carrier transmission functional group and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1272523A CN1272523A (en) | 2000-11-08 |
| CN1152942C true CN1152942C (en) | 2004-06-09 |
Family
ID=4585623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001162128A Expired - Fee Related CN1152942C (en) | 2000-05-30 | 2000-05-30 | Molecular twisty type electroluminescence material containing current carrier transmission functional group and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1152942C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12006344B2 (en) | 2016-05-24 | 2024-06-11 | Novo Nordisk A/S | MIC-1 compounds and use thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366703C (en) * | 2002-03-22 | 2008-02-06 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using same |
| US20070134243A1 (en) * | 2004-12-01 | 2007-06-14 | Gazzard Lewis J | Antibody drug conjugates and methods |
| CN101417996B (en) * | 2008-12-09 | 2013-04-10 | 苏州大学 | Compounds with symmetric structure containing carbazole and naphthalimide groups, preparation method and use thereof |
| DE102015108016A1 (en) * | 2015-01-20 | 2016-07-21 | Cynora Gmbh | Organic molecules, in particular for use in optoelectronic components |
| CN105384680A (en) * | 2015-11-10 | 2016-03-09 | 南京航空航天大学 | 9-(2'-aryl benzyl)-3, 6-diamino carbazole compound and preparation method thereof |
-
2000
- 2000-05-30 CN CNB001162128A patent/CN1152942C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12006344B2 (en) | 2016-05-24 | 2024-06-11 | Novo Nordisk A/S | MIC-1 compounds and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1272523A (en) | 2000-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1252215C (en) | Luminescent polymer | |
| CN1069659C (en) | Conjugated polymers having spiro centers and their use as electroluminescence materials | |
| RU2427058C1 (en) | Organic light-emitting device and display apparatus | |
| CN1416301A (en) | Organic electroluminescent element | |
| CN1490312A (en) | Carbazole Derivatives and Their Applications in Electroluminescent Devices | |
| CN1606393A (en) | Organic electroluminescent device | |
| CN1728902A (en) | Organic electroluminescent device | |
| CN101217187A (en) | An organic electroluminescent device with ultra-thin layer structure | |
| CN1555103A (en) | Organic/Polymer Light Emitting Diodes | |
| CN1152942C (en) | Molecular twisty type electroluminescence material containing current carrier transmission functional group and its application | |
| CN1449227A (en) | Organic electroluminescence device | |
| CN1202204C (en) | Red-light organic electroluminescent compound and components and devices made of it | |
| CN1241893A (en) | Organic electroluminescent device | |
| CN101170852B (en) | An organic electroluminescent device with ultra-thin layer structure | |
| CN101051673A (en) | Organic electroluminescence device capable of emitting green light, purple light and white light | |
| US7951965B2 (en) | Phenanthrene derivatives and organic light-emitting diodes containing said phenanthrene derivative | |
| CN101197427A (en) | A kind of white light organic electroluminescence device and its preparation method | |
| CN1921171A (en) | White light organic electroluminescent device | |
| CN1219018C (en) | Red fluorescent dye with star-shooting structure and synthetic method and application thereof | |
| CN101150902A (en) | Electroluminescent Devices Based on Pentacene as Hole Transport Layer | |
| CN1818010A (en) | Blue electroluminescent polymer and organic electroluminescent device using the same | |
| CN1317334C (en) | A kind of intramolecular charge transfer fluorescent dye and its application | |
| CN1239672C (en) | Electroluminescent phosphorescence material and its application | |
| CN1921717A (en) | Stacked organic electroluminescent element and manufacturing method thereof | |
| CN1743409A (en) | Capped thiophene small molecule and polymer materials, processing methods and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040609 |