CN104059090A - 一类吡啶和咔啉衍生物的合成方法及其应用 - Google Patents
一类吡啶和咔啉衍生物的合成方法及其应用 Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 230000005540 biological transmission Effects 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims 6
- 239000011521 glass Substances 0.000 claims 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 2
- 230000000903 blocking effect Effects 0.000 claims 2
- 239000002019 doping agent Substances 0.000 claims 2
- 238000002347 injection Methods 0.000 claims 2
- 239000007924 injection Substances 0.000 claims 2
- 150000003222 pyridines Chemical class 0.000 claims 2
- 230000027756 respiratory electron transport chain Effects 0.000 claims 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000005525 hole transport Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract 2
- 239000007787 solid Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 description 1
- RZFKFKHCMRGGGB-UHFFFAOYSA-N 2,4,6-tris(fluoromethyl)pyridine Chemical compound FCC1=CC(CF)=NC(CF)=C1 RZFKFKHCMRGGGB-UHFFFAOYSA-N 0.000 description 1
- MBTGBRYMJKYYOE-UHFFFAOYSA-N 2,6-difluoropyridine Chemical compound FC1=CC=CC(F)=N1 MBTGBRYMJKYYOE-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- 241000283074 Equus asinus Species 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract
本发明开发了一种原料廉价易得,无需加入贵金属催化剂,操作简便,反应条件温和,生产成本低,产率高,便于商业化的一步法合成吡啶和咔啉系列化合物的方法,涉及有机电致发光材料领域,具体涉及一步法合成一种具有双极载流子传输性能的材料及其做为电致磷光主体在电致发光领域的应用。将兼具空穴和电子传输能力的咔啉与吸电子基吡啶相连,获得电子和空穴传输更加平衡的主体材料2,6-二咔啉基吡啶,2,4,6-三咔啉基吡啶。
Description
技术领域
本发明涉及有机电致发光材料领域,具体涉及一步法合成一种具有双极载流子传输性能的材料及其做为电致磷光主体在电致发光领域的应用。
技术背景
1997年等在《Nature》上报道了首例以有机过渡金属配合物为发光体的有机电致磷光器件,发现电致磷光材料可同时利用单线态和三线态激子发光,其理论内量子效率可达到100%,引起了广泛关注和研究。近年来,基于磷光材料的有机电致发光二极管(OLED)由于其体积小质量轻、可挠曲、发光效率高、响应速度快等突出的优点而备受关注。然而,由于电致磷光材料本身较长的激发态寿命使得其本身存在严重的浓度淬灭和三重态-三重态湮灭效应,从而大大降低器件的发光效率和亮度。
现在的磷光电致发光器件中大多采用主客体结构,即将磷光发射物质以一定的浓度掺杂在主体物质中,以避免三重态-三重态的湮灭,提高磷光发射效率。
1999年Forrest和Thompson等[M.A.Baldo,S.Lamansky,P.E.Burroes,M.E.Thompson,S.R.Forrest.Appl Phys Let,1999,75,4.]将绿色磷光材料Ir(ppy)3以6wt%的浓度掺杂在4,4’-N,N’-二咔唑-联苯(CBP)的主体材料中,并引入了空穴阻挡层材料2,9-二甲基4,7-二苯基-1,10-邻菲罗啉(BCP),获得的绿光OLED最大外量子效率达8%,功率效率达31lm/W,均大大超过电致荧光发光器件,立即引起人们对主体材料的广泛关注。
2013年Jun Yeob Lee等[Chil Won Lee and Jun Yeob Lee Adv.Mater.2013,25,5450-5454]报导咔啉衍生物本身具有较高的三线态能级,且结构中因含有强吸电子基吡啶基团能提高主体材料的电子传输能力,将苯基咔唑与苯基咔啉通过suzuki偶联的方法获得获得双极主体材料CzBPCb,CbBPCb,通过间位连接保持较高的三线态能级,将蓝光材料Firpic与主体掺杂,器件EQE最大超过30%,是目前报导最高的蓝光磷光外量子效率。
咔啉类衍生物具有较好的电子传输性能和较高的三线态能级,由于咔啉结构中包含吡啶基团,使咔啉的电子传输能力强于咔唑,本发明中将咔啉单元和具有电子传输性能的吡啶单元以一定的方式连接,使主体的空穴和电子传输能力更加平衡,而传统方法形成碳氮键都需加入价格昂贵的贵金属催化剂,因此,本发明开发了一种原料廉价易得,无需加入贵金属催化剂,操作简便,反应条件温和,生产成本低,产率高,适合大规模生产的方法。制备了一类具有双极载流子传输性能的化合物,它们作为电致磷光器件发光层的主体材料,所制备的 蓝光器件最大电流效率高达44.2cd/A,最大能量效率38.5lm/W。
发明内容
本发明的目的在于提供一种高效、低廉、具有巨大商业价值的一步合成的方法获得具有双极载流子传输性能的材料和采用这种材料作为主体的高效电致磷光器件,该材料应用于电致磷光器件中,可获得高效的电致发光性能。
本发明所说的具有双极载流子传输性能的材料,将兼具空穴和电子传输能力的咔啉与吡啶相连,获得电子和空穴传输更加平衡的主体材料n-CbPy,结构如下所示:
具体实施方式
为了更好地理解本发明,下面通过具体的实施例来具体说明本发明的技术方案。
实施例1:2,6-二咔啉基吡啶(1)的合成
2,6-二氟吡啶(0.3g,2.6mmol),碳酸钾(2.2g,15.6mmol),咔啉(0.96g,5.7mmol),DMSO10ml,150℃加热回流12h。冷却至室温倒入200ml水中析出大量固体搅拌0.5h,抽滤得白色固体,柱层析提纯得白色固体0.75g,收率75%。1HNMR(CDCl3,400MHz):δppm8.59(d,2H,J=3.72Hz),8.46-8.41(m,4H),8.32(d,2H,J=7.76),8.24-8.20(m,1H),8.10(d,2H),7.43-7.32(m,6H).
实施例2:2,4,6-三咔啉基吡啶(2)的合成
2,4,6-三氟吡啶(0.3g,2.3mmol),其它同实例1,柱层析提纯得白色固体0.81g,收率61%。 1H NMR(CDCl3,400MHz):δppm8.95(s,2H),8.65(d,2H,J=8.40),8.59-8.57(m,3H),8.46-8.40(m,4H),8.18-8.11(m,3H),7.64(t,1H),7.49-7.31(m,8H).
表1为实施例(1)-(2)的器件数据,器件结构为:MoO3(5nm)/NPB(60nm)/TCTA(5nm)/ (1)-(2):Firpic(13%-18%,10nm)/TmPyPb(35nm)/CsCO3(2nm)。如表1所示制备的蓝光器件最大电流效率高达42.6cd/A最大能量效率37.12lm/W。
表1
Claims (9)
1.一种吡啶和咔啉类化合物,其结构式如下:
。
2.一种合成如权利要求1所述化合物的方法,其特征是在无需贵金属催化剂的条件下直接形成碳氮键,以及简便、高效条件温和的合成该类吡啶类化合物的通用方法,产物经多种方法检测与表征,产品纯度好,得率高,反应关键之步骤如下:
咔啉,氟代吡啶,碱,加入溶剂,氮气氛围回流5-12h,后处理直接通过乙醇重结晶或柱层析的方法分离提纯。
3.根据权利要求2所述的方法,其特征在于:所述有机溶剂为二甲亚砜或N,N-二甲基甲酰胺中的一种。
4.根据权利要求2所述的方法,其特征在于:所述碱是碳酸钾、氢氧化钠或叔丁醇钠中的一种。
5.根据权利要求1所述的化合物,兼具有空穴和电子传输性能的咔啉单元和具有电子传输性能的吡啶单元的化合物,作为蓝光磷光主体材料。
6.一种如权利要求1所述的化合物作为双极载流子传输材料的应用。
7.根据权利要求6所述的电致发光器件的应用,包括玻璃、附着在玻璃上的导电玻璃衬底层,与导电玻璃衬底层贴合的空穴注入层,与空穴注入层贴合的空穴传输层,与空穴传输层贴合的发光层,与发光层贴合的空穴阻挡层,与空穴阻挡层贴合的电子传输层,与电子传输层贴合的阴极层,其特征在于:所述发光层含有权利要求1所述的化合物。
8.根据权利要求7所述的电致发光器件,其特征在于:发光层由主体材料和掺杂材料组成,发光层的主体材料为权利要求1所述的化合物。
9.根据权利要求8所述的电致发光器件,其特征在于:掺杂材料为Firpic。
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CN104387369A (zh) * | 2014-10-28 | 2015-03-04 | 南京工业大学 | 一种热激活延迟荧光材料的合成方法及其应用 |
CN106810569A (zh) * | 2016-07-26 | 2017-06-09 | 浙江华显光电科技有限公司 | 一种咔啉三取代衍生物及其应用 |
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CN103570712A (zh) * | 2012-07-31 | 2014-02-12 | 乐金显示有限公司 | 磷光化合物和使用该磷光化合物的有机发光二极管器件 |
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CHIL WON LEE ET. AL.: "Above 30% External Quantum efficiency in Blue PHosphorescent Organic Light-Emitting Diodes Using Pyrido[2,3-b]indole Derivatives as Host Materials", 《ADVANCED MATERIALS》 * |
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CN104387369A (zh) * | 2014-10-28 | 2015-03-04 | 南京工业大学 | 一种热激活延迟荧光材料的合成方法及其应用 |
CN106810569A (zh) * | 2016-07-26 | 2017-06-09 | 浙江华显光电科技有限公司 | 一种咔啉三取代衍生物及其应用 |
CN106810569B (zh) * | 2016-07-26 | 2022-07-22 | 浙江华显光电科技有限公司 | 一种咔啉三取代衍生物及其应用 |
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