CN103936722B - Azophenlyene compounds that a kind of carbazole replaces and its production and use - Google Patents
Azophenlyene compounds that a kind of carbazole replaces and its production and use Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 22
- 230000005525 hole transport Effects 0.000 claims abstract description 21
- 238000005401 electroluminescence Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 37
- -1 phenazine compound Chemical group 0.000 claims description 29
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 25
- 150000002988 phenazines Chemical class 0.000 claims description 24
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 8
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 2
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000004893 oxazines Chemical class 0.000 claims 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 1
- 150000001716 carbazoles Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CCCC*[C@](CNC(CC(C)*C*)=C(C)NCC(C)C[*@@](C)C=CC=C)C=C Chemical compound CCCC*[C@](CNC(CC(C)*C*)=C(C)NCC(C)C[*@@](C)C=CC=C)C=C 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GYTMZTVZAXKTIW-UHFFFAOYSA-N C(C=CC=C1)c2c1c(cccc1)c1c(Nc1ccccc1)c2Nc1ccccc1 Chemical compound C(C=CC=C1)c2c1c(cccc1)c1c(Nc1ccccc1)c2Nc1ccccc1 GYTMZTVZAXKTIW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及一种吩嗪类化合物，特别是一种带有咔唑基团的吩嗪类化合物，以及该吩嗪类化合物的制备方法和用途。 The invention relates to a phenazine compound, especially a phenazine compound with a carbazole group, as well as a preparation method and application of the phenazine compound.
背景技术 Background technique
有机电致发光器件作为一种新型的显示技术，具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压等独特优点。自从1987年美国柯达公司的Tang等利用真空蒸镀超薄膜技术，以8-羟基喹啉铝(Alq3)作为发光层，三苯胺衍生物作为空穴传输层，与金属电极制成具有双层薄膜夹心式结构的低电压驱动有机电致发光器件（Tang C. W., Vanslyke S. A. Organic electroluminescent diodes. Appl. Phys. Lett. 1987, 51: 913-916）以来，人们对有机电致发光器件已经进行了很多研究。 As a new type of display technology, organic electroluminescent devices have unique advantages such as self-luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, and low driving voltage. Since 1987, Tang et al. of Kodak Corporation of the United States used vacuum evaporation ultra-thin film technology to use 8-hydroxyquinoline aluminum (Alq 3 ) as the light-emitting layer, triphenylamine derivatives as the hole transport layer, and a metal electrode to make a double layer Since Low Voltage Driven Organic Electroluminescent Diodes with Thin Film Sandwich Structure (Tang CW, Vanslyke SA Organic electroluminescent diodes. Appl. Phys. Lett. 1987, 51: 913-916), people have done a lot of research on organic electroluminescent diodes. Research.
有机电致发光器件的发光原理是当施加电场时，正负电荷分别由阳极和阴极注入到空穴传输层和电子传输层，然后在发光层中复合并使发光物质发光。因此，要提高器件的效率，需要提高电荷注入空穴传输层和电子传输层的效率。这些年，人们已经研究了各种空穴传输材料和电子传输材料，有机电致发光材料和器件已经广泛地应用在手机以及小屏幕的显示面板上。但是，有机电致发光材料的稳定性和器件的寿命仍然是制约其应用的重要因素，且空穴传输材料仍然是影响器件的一个重要因素。 The luminescent principle of organic electroluminescent devices is that when an electric field is applied, positive and negative charges are injected from the anode and cathode into the hole transport layer and the electron transport layer respectively, and then recombine in the luminescent layer to make the luminescent material emit light. Therefore, to increase the efficiency of the device, it is necessary to increase the efficiency of charge injection into the hole transport layer and the electron transport layer. In recent years, various hole transport materials and electron transport materials have been studied, and organic electroluminescence materials and devices have been widely used in mobile phones and display panels of small screens. However, the stability of organic electroluminescent materials and the lifetime of devices are still important factors restricting their applications, and hole transport materials are still an important factor affecting devices.
NPB(N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺)作为一种空穴传输材料，从发明到现在，一直被大量的研究应用，但是其稳定性和导电能力仍需提高。 NPB (N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4-4′-diamine), as a hole transport material, was invented from Up to now, it has been widely studied and applied, but its stability and conductivity still need to be improved.
吩嗪类化合物具有良好的空穴传输性能，苏建华等报道了新的吩嗪类化合物的合成方法，如CN 102491950中下述结构的化合物，极大地推动了酚嗪的产业化进程。本发明就是在其合成工艺的基础上，在吩嗪上引入一个咔唑基团，同原文献相比，化合物的稳定性得到提高且空穴传输性能增强。 Phenazine compounds have good hole transport properties. Su Jianhua et al. reported a new synthesis method for phenazine compounds, such as the compound with the following structure in CN 102491950, which greatly promoted the industrialization process of phenazines. The present invention introduces a carbazole group on the phenazine on the basis of its synthesis process. Compared with the original document, the stability of the compound is improved and the hole transport performance is enhanced.
发明内容 Contents of the invention
本发明的目的在于提供一系列具有较好热稳定性的咔唑取代的吩嗪类化合物及其制备方法。 The object of the present invention is to provide a series of carbazole-substituted phenazine compounds with good thermal stability and a preparation method thereof.
本发明的目的还在于将所述吩嗪类化合物作为有机电致发光空穴传输或注入材料，应用在有机电致发光器件上。由本发明所述材料制备的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。 The purpose of the present invention is also to use the phenazine compound as an organic electroluminescent hole transport or injection material in an organic electroluminescent device. The organic electroluminescence device prepared by the material of the present invention has the advantages of good electroluminescence efficiency, excellent color purity and long life.
本发明所述的咔唑取代的吩嗪类化合物为具有式(I)所述结构通式的化合物： The carbazole-substituted phenazine compound of the present invention is a compound having the general structural formula described in formula (I):
其中，Ar1、Ar2各自独立地表示为C1～C4取代或未取代的苯，萘，吡啶，噻吩或喹啉。 Wherein, Ar1 and Ar2 each independently represent C 1 -C 4 substituted or unsubstituted benzene, naphthalene, pyridine, thiophene or quinoline.
本发明结构通式(I)所述的吩嗪类化合物由结构通式(II)所述的卤代吩嗪与结构通式(III)所述的咔唑类衍生物为原料制备得到： The phenazine compounds described in the general structural formula (I) of the present invention are prepared from the halogenated phenazines described in the general structural formula (II) and the carbazole derivatives described in the general structural formula (III):
其中X表示为Cl、Br或I； Wherein X is represented as Cl, Br or I;
其中，Ar1、Ar2各自独立地表示为C1～C4取代或未取代的苯，萘，吡啶，噻吩或喹啉。 Wherein, Ar1 and Ar2 each independently represent C 1 -C 4 substituted or unsubstituted benzene, naphthalene, pyridine, thiophene or quinoline.
本发明结构通式(I)所述吩嗪类化合物的具体制备方法是： The specific preparation method of the phenazine compounds described in general structural formula (I) of the present invention is:
以结构通式(II)所述的卤代吩嗪与结构通式(III)所述的咔唑类衍生物为原料，在钯催化和碱存在下，于80～120℃进行Buchwald-Hartwig反应8～10小时，得到结构通式(I)所述的吩嗪类化合物。 Using the halogenated phenazines described in the general structural formula (II) and the carbazole derivatives described in the general structural formula (III) as raw materials, the Buchwald-Hartwig reaction is carried out at 80-120°C in the presence of palladium catalysis and alkali After 8-10 hours, the phenazine compound described in general structural formula (I) is obtained.
其中，所述结构通式(II)所述的卤代吩嗪、结构通式(III)所述的咔唑类衍生物、钯催化剂和碱的物质的量比为1︰1︰0.01︰1.5。 Wherein, the molar ratio of the halogenated phenazine described in the general structural formula (II), the carbazole derivative described in the general structural formula (III), the palladium catalyst and the base is 1:1:0.01:1.5 .
所述的碱选自碱金属碳酸盐、碱金属磷酸盐、碱金属氢氧化物或叔丁醇碱金属盐。 The base is selected from alkali metal carbonate, alkali metal phosphate, alkali metal hydroxide or alkali metal tert-butoxide.
所述的钯催化剂选自醋酸钯、二氯化钯、四(三苯基磷)钯、[1,1′-双(二苯基膦)二茂铁]二氯化钯(II)中的一种。 The palladium catalyst is selected from palladium acetate, palladium dichloride, tetrakis (triphenylphosphine) palladium, [1,1'- bis (diphenylphosphine) ferrocene] palladium dichloride (II ) in one.
本发明结构通式(I)所述吩嗪类化合物还可以通过下述方法制备： The phenazine compounds described in general structural formula (I) of the present invention can also be prepared by the following method:
以结构通式(II)所述的卤代吩嗪与结构通式(III)所述的咔唑类衍生物为原料，在铜催化和碱存在下，于120～200℃进行Ullmman反应8～10小时，得到结构通式(I)所述的吩嗪类化合物。 Using the halogenated phenazines described in the general structural formula (II) and the carbazole derivatives described in the general structural formula (III) as raw materials, in the presence of copper catalysis and alkali, carry out the Ullmman reaction at 120-200 ° C for 8- After 10 hours, the phenazine compound described in general structural formula (I) was obtained.
其中，所述结构通式(II)所述的卤代吩嗪、结构通式(III)所述的咔唑类衍生物、铜催化剂和碱的物质的量比为1︰1︰0.01︰1.5。 Wherein, the molar ratio of the halogenated phenazine described in the general structural formula (II), the carbazole derivative described in the general structural formula (III), the copper catalyst and the base is 1:1:0.01:1.5 .
所述的碱选自碱金属碳酸盐、碱金属磷酸盐、碱金属氢氧化物或叔丁醇碱金属盐。 The base is selected from alkali metal carbonate, alkali metal phosphate, alkali metal hydroxide or alkali metal tert-butoxide.
所述的铜催化剂选自卤化亚铜、卤化铜、硫酸铜、乙酸铜、铜粉或氧化铜中的一种。 The copper catalyst is selected from one of cuprous halide, copper halide, copper sulfate, copper acetate, copper powder or copper oxide.
本发明所述结构通式(I) 吩嗪类化合物制备方法的反应式如下： The reaction formula of the general structural formula (I) phenazine compounds preparation method of the present invention is as follows:
X表示为Cl或者Br或者I。Ar1、Ar2各自独立地表示为C1～C4取代或未取代的苯，萘，吡啶，噻吩或喹啉。 X is represented as Cl or Br or I. Ar1 and Ar2 each independently represent C 1 -C 4 substituted or unsubstituted benzene, naphthalene, pyridine, thiophene or quinoline.
以下(1)～(11)列举了部分符合结构通式(I)的吩嗪类化合物的具体结构式，但需要说明的是，下述列举的结构式并不构成对本发明所述吩嗪类化合物的限定： Following (1)～(11) have enumerated the specific structural formula of the phenazine compounds that part meets general structural formula (I), but it should be noted that, the structural formula enumerated below does not constitute the reference to the phenazine compounds of the present invention. limited:
。 .
本发明制备得到的吩嗪类化合物具有较好的热稳定性，可以作为有机电致发光空穴传输材料或者空穴注入材料，应用于有机电致发光器件上。 The phenazine compounds prepared by the invention have good thermal stability, and can be used as organic electroluminescent hole transport materials or hole injection materials and applied to organic electroluminescent devices.
同样，本发明制备得到的吩嗪类化合物也可以作为发光层材料，应用于有机电致发光器件上。 Similarly, the phenazine compounds prepared in the present invention can also be used as light-emitting layer materials and applied to organic electroluminescent devices.
本发明还提供了包括有上述吩嗪类化合物的有机电致发光器件。 The present invention also provides an organic electroluminescent device comprising the above-mentioned phenazine compound.
所述有机电致发光器件由基板、阴阳电极和设置在阴阳电极之间的有机层构成，其中有机层包括发光层、电子传输层、空穴传输层、空穴注入层、电子注入层等，需要特别指出的是，上述有机层可以根据需要进行选择，不必每层都存在。 The organic electroluminescent device is composed of a substrate, cathode and anode electrodes, and an organic layer arranged between the anode and cathode electrodes, wherein the organic layer includes a light emitting layer, an electron transport layer, a hole transport layer, a hole injection layer, an electron injection layer, etc., It should be pointed out that the above-mentioned organic layers can be selected according to needs, and it is not necessary for every layer to exist.
具体地，本发明的有机电致发光器件是在器件的阴阳电极之间至少包含有一层含有结构通式(I)所述吩嗪类化合物的有机层。 Specifically, the organic electroluminescence device of the present invention includes at least one organic layer containing the phenazine compound described in the general structural formula (I) between the cathode and anode electrodes of the device.
进而，本发明所述的有机电致发光器件是至少包含有一层含有结构通式(I)所述吩嗪类化合物的空穴传输层或空穴注入层。 Furthermore, the organic electroluminescence device of the present invention comprises at least one hole transport layer or hole injection layer containing the phenazine compound described in the general structural formula (I).
本发明所述结构通式(I)所述的吩嗪类化合物还可以包含在有机电致发光器件的发光层内。 The phenazine compound described in the general structural formula (I) of the present invention can also be included in the light-emitting layer of the organic electroluminescent device.
本发明中，所述有机电致发光器件的有机层厚度为50～1000nm，优选为100～500nm。 In the present invention, the thickness of the organic layer of the organic electroluminescence device is 50-1000 nm, preferably 100-500 nm.
所述的空穴传输层和空穴注入层的厚度为10～1000nm，优选为30～200nm。 The thickness of the hole transport layer and the hole injection layer is 10-1000 nm, preferably 30-200 nm.
所述含有结构通式(I)所述吩嗪类化合物的有机层可以通过真空蒸镀或者旋涂方式沉积在电极上。 The organic layer containing the phenazine compound described in the general structural formula (I) can be deposited on the electrode by vacuum evaporation or spin coating.
对所述有机电致发光器件进行实验测试表明，本发明结构通式(I)所述吩嗪类化合物作为有机电致发光材料具有较好的热稳定性、高发光效率和高发光纯度。使用所述有机电致发光材料制作的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。 Experimental testing of the organic electroluminescent device shows that the phenazine compound described in the general structural formula (I) of the present invention has good thermal stability, high luminous efficiency and high luminous purity as an organic electroluminescent material. The organic electroluminescence device made by using the organic electroluminescence material has the advantages of good electroluminescence efficiency, excellent color purity and long service life.
附图说明 Description of drawings
图1为本发明实施例2有机电致发光器件的器件结构图，图中10为玻璃基板，20为阳极，30为空穴传输层，40为发光层，50为电子传输层，60为电子注入层，70为阴极。 Fig. 1 is the device structural diagram of the organic electroluminescent device of embodiment 2 of the present invention, among the figure 10 is a glass substrate, 20 is an anode, 30 is a hole transport layer, 40 is a light-emitting layer, 50 is an electron transport layer, and 60 is an electron The injection layer, 70 is the cathode.
图2为实施例2有机电致发光器件在7V电压下的发射光谱图。 Fig. 2 is an emission spectrum diagram of the organic electroluminescent device in Example 2 at a voltage of 7V.
具体实施方式 detailed description
实施例1 Example 1
原料1 raw material 1
向加有20mL甲苯的50mL单口烧瓶中加入0.0045g醋酸钯和0.0058g三叔丁基磷，溶解后，氮气保护下再依次加入0.5g购自上海道亦化工科技有限公司的原料1、0.3g咔唑和0.22g叔丁醇钾，加热回流过夜。反应完全后，过滤，水洗，滤液旋蒸除去溶剂，硅胶柱层析分离，得到280mg吩嗪类化合物白色固体，产率47%。 Add 0.0045g of palladium acetate and 0.0058g of tri-tert-butylphosphine into a 50mL single-necked flask with 20mL of toluene. After dissolving, add 0.5g of raw materials 1 and 0.3g purchased from Shanghai Daoyi Chemical Technology Co., Ltd. under nitrogen protection. Carbazole and 0.22g potassium tert-butoxide, heated to reflux overnight. After the reaction was complete, filter and wash with water, the filtrate was rotary evaporated to remove the solvent, and separated by silica gel column chromatography to obtain 280 mg of phenazine compounds as a white solid with a yield of 47%.
1H NMR (400 MHz, CDCl3) δ 8.84 – 8.77 (m, 2H), 8.39 – 8.34 (m, 1H), 8.21 (d, J = 8.1 Hz, 1H), 8.10 (d, J = 7.6 Hz, 2H), 7.84 (m, 2H), 7.73 (m, 3H), 7.61 (t, J = 7.6 Hz, 1H), 7.46 – 7.41 (m, 2H), 7.35 (t, J = 7.7 Hz, 2H), 7.23 (t, J = 7.5 Hz, 2H), 7.16 – 6.99 (m, 10H), 6.86 (t, J = 7.2 Hz, 1H)。HRMS(ESI, m/z)：计算值[M+H]+ C44H29N3，600.2440；实测值600.2443。 1 H NMR (400 MHz, CDCl 3 ) δ 8.84 – 8.77 (m, 2H), 8.39 – 8.34 (m, 1H), 8.21 (d, J = 8.1 Hz, 1H), 8.10 (d, J = 7.6 Hz, 2H), 7.84 (m, 2H), 7.73 (m, 3H), 7.61 (t, J = 7.6 Hz, 1H), 7.46 – 7.41 (m, 2H), 7.35 (t, J = 7.7 Hz, 2H), 7.23 (t, J = 7.5 Hz, 2H), 7.16 – 6.99 (m, 10H), 6.86 (t, J = 7.2 Hz, 1H). HRMS (ESI, m/z): Calcd. for [M+H] + C44H29N3 , 600.2440 ; found 600.2443 .
实施例2 Example 2
本实施例提供了一种含有实施例1吩嗪类化合物的有机电致发光器件，所述吩嗪类化合物在该器件中作为空穴传输层材料使用，其器件结构为： This embodiment provides an organic electroluminescent device containing a phenazine compound in Example 1, the phenazine compound is used as a hole transport layer material in the device, and its device structure is:
ITO/实施例1吩嗪类化合物(60nm)/ Alq3(30nm)/ Alq3(10nm)/LiF(1nm)/Al(100nm)。 ITO/Example 1 Phenazine compound (60nm)/Alq 3 (30nm)/Alq 3 (10nm)/LiF (1nm)/Al (100nm).
首先，将透明导电ITO玻璃基板10(上面带有阳极20)依次经洗涤剂、去离子水、乙醇、丙酮和去离子水洗净，再用氧等离子体处理30秒，接着用等离子处理的CFx处理；然后在ITO玻璃基板上蒸镀实施例1吩嗪类化合物，形成60nm厚的空穴传输层30；顺序在空穴传输层上蒸镀30nm厚的Alq3作为发光层40，在发光层上蒸镀10nm厚的Alq3作为电子传输层50，蒸镀1nm厚的LiF作为电子注入层60，最后，蒸镀100nm厚的Al作为器件阴极70。 First, the transparent conductive ITO glass substrate 10 (with the anode 20) is washed sequentially through detergent, deionized water, ethanol, acetone and deionized water, and then treated with oxygen plasma for 30 seconds, and then treated with plasma treated CFx treatment; then on the ITO glass substrate, evaporate the phenazine compounds of Example 1 to form a 60nm thick hole transport layer 30; sequentially evaporate 30nm thick Alq 3 on the hole transport layer as the light emitting layer 40, on the light emitting layer 10nm-thick Alq3 was vapor-deposited on it as the electron transport layer 50 , 1nm-thick LiF was vapor-deposited as the electron-injection layer 60 , and finally, 100nm-thick Al was vapor-deposited as the device cathode 70 .
上述制备的有机电致发光器件在7V电压下的效率为2.06cd/A，发绿光，图2为其在7V电压下的发射光谱。 The organic electroluminescent device prepared above has an efficiency of 2.06 cd/A at a voltage of 7V and emits green light. Figure 2 shows its emission spectrum at a voltage of 7V.
比较例1 Comparative example 1
以NPB作为空穴传输层材料，制备有机电致发光器件，其器件结构为： Using NPB as the material of the hole transport layer, an organic electroluminescence device is prepared, and its device structure is as follows:
ITO/NPB(60nm)/ Alq3(30nm)/ Alq3(10nm)/LiF(1nm)/Al(100nm)。制备方法同时实施例2。 ITO/NPB(60nm)/ Alq3 (30nm)/ Alq3 (10nm)/LiF(1nm)/Al(100nm). The preparation method is the same as Example 2.
所制备的有机电致发光器件在7V电压下的效率为1.87cd/A，发绿光。 The prepared organic electroluminescent device has an efficiency of 1.87cd/A at a voltage of 7V and emits green light.
由此可见，在相同条件下，本发明制备的有机电致发光器件的发光效率高于比较例，本发明有机电致发光材料具有高的稳定性，以其制备的有机电致发光器件具有高的效率和光纯度。 This shows that under the same conditions, the luminous efficiency of the organic electroluminescent device prepared by the present invention is higher than that of the comparative example, the organic electroluminescent material of the present invention has high stability, and the organic electroluminescent device prepared by it has high efficiency and light purity.
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