CN1246417C - Electroluminescent organic material and its application - Google Patents

Electroluminescent organic material and its application Download PDF

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CN1246417C
CN1246417C CN 02116538 CN02116538A CN1246417C CN 1246417 C CN1246417 C CN 1246417C CN 02116538 CN02116538 CN 02116538 CN 02116538 A CN02116538 A CN 02116538A CN 1246417 C CN1246417 C CN 1246417C
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CN1376758A (en
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邱勇
乔娟
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清华大学
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Abstract

本发明涉及一种有机电致发光材料及其应用,属于电子材料技术领域。 The present invention relates to an organic electroluminescent material and its application, it belongs to the technical field of electronic materials. 该材料是一种中心原子是镓原子的含有三齿配体的五配位的金属配合物,其特征在于,该材料具有以下结构,其中I、Ⅱ、Ⅲ分别代表芳香环或者杂环化合物及其取代的衍生物。 This material is a central metal atom-containing five-coordinate complexes tridentate ligand gallium atoms, wherein the material has a structure in which the I, Ⅱ, Ⅲ represent an aromatic ring or a heterocyclic compound, and substituted derivatives thereof. 本发明中的材料具有玻璃化温度高、热稳定性好,容易形成良好的无定形薄膜,在溶液和固体膜中都有较强的荧光,且荧光量子效率高等优点,本材料可优先传输电子、阻挡空穴,并且还可以用作发光体,包括单独作发光层,或者作为本体掺杂染料发光,或者作为掺杂染料而发光。 In the present invention, a material having a high glass transition temperature, good thermal stability, good easy to form an amorphous thin film in the solution and the solid film has strong fluorescence, and the fluorescence quantum efficiency advantages of the present electron-transporting material may be preferentially , blocking holes, and may also be used as a light emitter, a light emitting layer comprising as alone or as a dye-doped light emitting body or light-emitting dye as a dopant.

Description

一种有机电致发光材料及其应用 An organic electroluminescent material and its application

技术领域 FIELD

:本发明涉及一种有机电致发光材料,属于电子材料技术领域。 : The present invention relates to an organic electroluminescent material, it belongs to the technical field of electronic materials.

背景技术 Background technique

:当今,随着多媒体技术的发展和信息社会的来临,对平板显示器性能的要求越来越高。 : Today, with the advent of multimedia technology and the development of information society, the demand for higher and higher performance flat panel displays. 近年新出现的三种显示技术:等离子显示器、场发射显示器和有机电致发光显示器(OLED),均在一定程度上弥补了阴极射线管和液晶显示器的不足。 In recent years, three kinds of emerging display technologies: plasma displays, field emission displays and organic electroluminescent displays (the OLED), were up for the lack cathode ray tubes and liquid crystal display to a certain extent. 其中,OLED具有自主发光、低电压直流驱动、全固化、视角宽、颜色丰富等一系列的优点,与液晶显示器相比,OLED不需要背光源,视角大,功率低,其响应速度达液晶显示器的1000倍,其制造成本却低于同等分辨率的液晶显示器,因此,有机电致发光显示器势必具有广阔的应用前景。 Wherein, the OLED has a light emission independent, low voltage DC drive, fully cured, wide viewing angle, color and rich series of advantages, compared with liquid crystal displays, OLED does not need a backlight, a large viewing angle, low power, the response speed of the liquid crystal display 1000 times, its manufacturing costs are lower than the same resolution liquid crystal display, therefore, is bound to an organic electroluminescent display having a wide application prospect.

OLED的典型结构包括阴极层、阳极层,和位于这两层之间的有机功能层,有机功能层中可包括电子传输层、空穴传输层和发光层中的一种或几种功能层。 A typical structure of an OLED comprising a cathode layer, an anode layer, an organic functional layer located between the two layers, the organic functional layer may comprise an electron transport layer, a hole transport layer and the light emitting layer one or more functional layers. 相应的用于有机电致发光的材料,也可根据其在器件中所承担的功能可分为:电子传输材料、空穴传输材料和发光材料三大类。 Corresponding with a material for organic electroluminescence, it may be grouped according to their assumed in the device features: electron transport material, hole transport material and a light emitting material three categories. 1987年美国柯达公司的CWTang等人采用双层结构以8-羟基喹啉铝(Alq3)作发光层,以芳香二胺作为空穴传输层,得到了直流低电压驱动的高亮度有机EL器件。 Kodak company in 1987, who used a double structure CWTang to 8-hydroxyquinoline aluminum (Alq3) as a light-emitting layer to the hole transport layer as aromatic diamines, to obtain a high luminance of the organic EL device of low-voltage DC drive. 这一突破性进展使有机电致发光器件成为当前发光器件研究的热点。 This breakthrough so that the organic electroluminescent device become a research focus of the light emitting device. 其中8-羟基喹啉铝兼有发光和电子传输两大功能,它的采用具有开创性的历史意义(Appl.Phys.Lett.,1987,51(913);Coordination Chemistry Reviews,171(1998)161-174)。 8-hydroxyquinoline aluminum wherein both light emission and electron transport two functions, it uses a groundbreaking historical significance (Appl.Phys.Lett, 1987,51 (913);. Coordination Chemistry Reviews, 171 (1998) 161 -174). 但是Alq3本身的荧光量子效率和电致发光效率还是比较低的,有机电致发光技术的发展还有赖于新型的电致发光材料的开发和器件结构的完善。 However, the fluorescence quantum efficiency and Alq3 itself electroluminescent electrical efficiency is relatively low, the development of organic electroluminescent light emitting novel technique also depends on the development and improvement of electroluminescent device structure of the light emitting material.

随之许许多多的8-羟基喹啉铝的衍生物被开发出来并用于有机电致发光器件的研究中,其中大多是对其配体上作修饰以改进其性能。 Derivatives of 8-hydroxyquinoline aluminum consequent many have been developed and used for research in organic electroluminescent devices, most of which are made on which the ligand is modified to improve its performance. Y.Hamada(IEEE transactions on electron devices,1997,44,1208)首次创新性引入水杨醛缩亮氨酸作为三齿配体,虽然在溶液中在观察到了强烈的蓝色荧光,却没有得到固体的发光材料。 Y.Hamada (IEEE transactions on electron devices, 1997,44,1208) first introduced innovative salicylaldehyde leucine as tridentate ligands, although in solution was observed a strong blue fluorescence, but did not give a solid the luminescent material. 邵炎等人在专利CN1258710A中采用稳定的芳香三齿配体代替了原来的脂肪类三齿配体,得到了热稳定性和成膜性有很大提高的(水杨醛缩邻胺苯酚)-(8-羟基喹啉)合铝(III)(Al(Saph)-q)及其衍生物。 Shao Yandeng employed in the patent CN1258710A stable Aromatic tridentate ligand instead of the original fat tridentate ligands to obtain a film-forming properties and thermal stability greatly improved (salicylaldehyde-o-aminophenol) - (8-hydroxyquinoline) aluminum (III) (Al (Saph) -q), and derivatives thereof. 在文献中也有报道(Chem.Lett.,2000,1068-1069和Adv.Mater.Opt.Electron.,10(6),283-286),采用邻羟基芳香醛缩邻羟基芳香胺作为三齿配体,取代了Alq3中两个8-羟基喹啉配体,可增加分子的不对称性,从而提高的材料的成膜性能。 Has also been reported in the literature (Chem.Lett., 2000,1068-1069 and Adv.Mater.Opt.Electron., 10 (6), 283-286), using o-hydroxy-o-hydroxy aromatic aldehydes aromatic amine as a tridentate ligand body, instead of Alq3 in two 8-quinolinol ligand molecules increase asymmetry, thereby improving film-forming properties of the material. 但现有专利技术中Al(Saph)-q及其衍生物的中心金属离子仍然采用的是金属铝,经实验证明其产品纯化很困难。 However, the prior art patents central metal ion Al (Saph) -q and its derivatives is still used metal aluminum, which product is purified by proved very difficult.

另一类8-羟基喹啉铝的衍生物是改换其中心金属离子,如采用Zn、Mg、Be、Ga、In来替换Al,这样对配合物的发光颜色、效率和稳定性均会有一定的改变,经实验比较,其中综合性能较好的主要是中心金属离子为Ga、Zn和Be的配合物。 Another class of derivatives of 8-hydroxyquinoline aluminum change its center is a metal ion, such as use of Zn, Mg, Be, Ga, In replacing Al, so that the emission color of the complex, all have some efficiency and stability changes, the experiments, the better overall performance which is mainly the central metal ion is Ga, Zn, and be complexes. 8-羟基喹啉镓(Gaq3)的发光颜色为黄绿色,谱峰在553nm左右,具有较高的亮度。 8-hydroxyquinoline gallium (Gaq3) of yellowish green color emission spectrum peak at about 553 nm, has a high luminance. PEBurrowsd等人(.Appl.Phys.Lett.64(20),1994)对比研究了Al、Ga、In、Sc的8-羟基喹啉金属配合物,发现在同样的器件结构(ITO/TPD(20nm)/Mq3(40nm)/Mg∶Ag)下,采用Gaq3的器件不仅表现了与Alq3的器件相当的外量子效率,而且具有更低的启亮电压和更高的能量效率(比Alq3的器件高出50%)。 Comparative PEBurrowsd et al (.Appl.Phys.Lett.64 (20), 1994) studied Al, Ga, In, Sc of 8-hydroxyquinoline metal complexes found in the same device structure (ITO / TPD (20nm under) / Mq3 (40nm) / Mg:Ag), using not only the device Gaq3 Alq3 device with corresponding external quantum efficiency, but also has a lower voltage and a higher energy Qiliang efficiency (higher than Alq3 devices 50%). Shuit-tong Lee等人(J.Phys.D.34,30-35,2001)对比研究了以Al、Ga和In为中心金属离子的8-羟基喹啉金属配合物分别作为本体材料,掺杂红光染料4-4-二氰基亚甲基-2-叔丁基-6-(1,1,7,7-四甲基-久洛尼定-9-乙烯基)-4H-吡喃(DCJMTB),使用N,N'-二苯基-N,N'-双(间甲基苯基)-1,1'-联苯基-4,4'-二胺(TPD)作为空穴传输材料的红色电致发光器件(ITO/TPD/MQ3∶DCJMTB/MQ3/Mg∶Ag)的性能,结果同样发现使用Gaq3作本体掺杂DCJMTB的器件具有饱和的红光发射,且有更高的电流效率,超过了Alq3作本体掺杂DCJMTB的器件。 Shuit-tong Lee et al. (J.Phys.D.34,30-35,2001) In a comparative study of Al, Ga and In as the central metal ion of 8-quinolinol metal complexes, respectively, as a bulk material, doped red dye 4-4- dicyanomethylene-2-t-butyl-6- (1,1,7,7-tetramethyl - julolidine-9-vinyl) -4H- pyran (DCJMTB), using N, N'- diphenyl -N, N'- bis (m-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD) as the hole red electroluminescent material transport electroluminescent device (ITO / TPD / MQ3:DCJMTB / MQ3 / Mg:Ag) performance and the results also found use as a body dopant DCJMTB Gaq3 device having a saturated red emission, and higher current efficiency than the device body dopant Alq3 as the DCJMTB. 另外,Sapochak(J.Phys.Chem,100,17766-17771)和Andreas Elschner(Adv.Mater.23,(3),1811,2001)等人报道了对2-甲基取代的8-羟基喹啉镓的五配位化合物的研究,发现其也表现出很好的电致发光性能。 Further, Sapochak (J.Phys.Chem, 100,17766-17771) and Andreas Elschner (Adv.Mater.23, (3), 1811,2001), who reported on the methyl-substituted 8-hydroxyquinoline Study five gallium complex compound, which is also found to exhibit excellent electroluminescent properties. 由此可见,在众多试图替代Alq3的材料中,金属镓的配合物表现了优越的性能,被公认为是最有希望的一类材料。 Thus, many attempts to replace the material of Alq3, metal gallium complexes show superior performance, is recognized as the most promising class of materials. 因此对新型的金属镓的配合物进行深入的研究是非常有意义的。 Therefore, a new type of metal gallium complex in-depth study is very significant.

发明内容 SUMMARY

:本发明的目的是提出一种新型的有机电致发光材料,该材料为金属配合物,可以改善现有技术中的以8-羟基喹啉为配体的金属配合物和以Al为中心金属离子的金属配合物存在的问题,本发明目的是提高材料的荧光量子效率和电致发光效率,改善材料成膜性能,克服材料易结晶的缺点,并保证材料容易提纯。 : Object of the present invention is to provide a novel organic electroluminescent material which is a metal complex, the prior art can be improved to 8-quinolinol as a ligand in metal complexes and Al as a central metal metal complex ion present problems, an object of the invention is to improve the drawback of fluorescence quantum efficiency and electroluminescence efficiency, improve film formation properties of the material, the material easily overcome crystalline material, and to ensure that material is easily purified.

本发明提出了一种新型的有机电致发光材料,该材料是一种中心原子是镓原子的具有三齿配体的金属配合物,其特征在于,该发光材料具有下面所示结构: The present invention provides a novel organic electroluminescent material which is a gallium atom is a central metal atom having a tridentate ligand complexes, characterized in that the luminescent material has the structure shown below:

上述结构式中,I、II、III分别代表芳香环或者杂环化合物及其取代的衍生物,其中I处的芳香环可以为8-羟基喹啉、4-羟基-1,5-萘啶、5-羟基-喹喔啉、2-(2-羟基苯基)苯并噁唑、2-(2-羟基苯基)苯并咪唑、2-(2-羟基苯基)苯并噻唑、10-羟基苯并喹啉或吡啶-2-甲酸中的一种;II、III处的芳香环可以为苯环、萘环或菲环中的一种,或者为含有杂原子的芳香环如吡啶、噻唑或咔唑中的一种,其中I、II、III上可以有一个或多个取代基,取代基可以是氢原子、烷基、异烷基、烷氧基、硝基、氰基、氨基、卤素原子、芳香基、呋喃、噻吩、吡咯或吡啶中的一种。 In the above formulas, I, II, III respectively represent an aromatic ring or a heterocyclic compound and substituted derivatives thereof wherein the aromatic ring of I at the 8-hydroxyquinoline may be, 4-hydroxy-1,5, 5 - hydroxy - quinoxaline, 2- (2-hydroxyphenyl) benzoxazole, 2- (2-hydroxyphenyl) benzimidazole, 2- (2-hydroxyphenyl) benzothiazole, 10-hydroxy or benzo-quinoline-carboxylic acid pyridine-2-one kind of; aromatic ring II, III may be at the benzene ring, a naphthalene ring or phenanthrene ring one kind, or a hetero atom-containing aromatic ring such as pyridine, thiazole or one kind carbazole, wherein the I, II, III may have one or more substituents, the substituent may be a hydrogen atom, an alkyl, isoalkyl, alkoxy, nitro, cyano, amino, halo atoms, aryl, furan, thiophene, pyrrole or a pyridine.

本发明的有机电致发光材料结构通式中,其中的配体I可以为8-羟基喹啉、4-羟基-1,5-萘啶、5-羟基-喹喔啉、2-(2-羟基苯基)苯并噁唑、2-(2-羟基苯基)苯并咪唑、2-(2-羟基苯基)苯并噻唑、10-羟基苯并喹啉或吡啶-2-甲醛等中的一种。 The present invention is an organic electroluminescent light emitting material in the structural formula, wherein ligand I may be 8-hydroxyquinoline, 4-hydroxy-1,5, 5-hydroxy - quinoxaline, 2- (2- hydroxyphenyl) benzoxazole, 2- (2-hydroxyphenyl) benzimidazole, 2- (2-hydroxyphenyl) benzothiazole, or a 10-hydroxybenzo quinoline-2-carbaldehyde and the like a. 其中I上的取代基可以是氢原子、烷基、异烷基、烷氧基、硝基、氰基、氨基、卤素原子、芳香基、呋喃、噻吩、吡咯或吡啶中的一种。 Wherein the substituents on the I can be a hydrogen atom, an alkyl group, an isobutyl group, an alkyl group, a nitro group, a cyano group, an amino group, a halogen atom, an aromatic group, furan, thiophene, pyrrole or pyridine.

根据配体I结构的不同,本发明的发光材料大致有8类结构,如以下结构式i-viii所示: Depending on the ligand structure I, the luminescent material according to the present invention generally has a class structure 8, as shown in the following structural formulas i-viii:

如上所示结构i-viii中,当配体II、III分别都为苯环时为优选的典型化合物,即化合物i-1-viii-1,结构其如下所示: I-viii structure shown above, when ligands II, III typical compounds are benzene rings are preferred, i.e. compound i-1-viii-1, the structure of which is as follows: 结构式为i的化合物,当其中配体I为8-羟基喹啉,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的25种化合物i-1-i-25结构如下所示: The compound of formula i, wherein when the ligand is 8-hydroxyquinoline I, ligand II, III, respectively, a benzene ring, a naphthalene ring or a phenanthrene ring, condensed ring and substituted derivatives thereof, preferably the 25 compounds i -1-i-25 structure is as follows:

结构通式为i的化合物,当其中配体I是取代的8-羟基喹啉,配体II,III均为苯环时,优选的化合物i-26-i-35结构如下: Structural formula of compound i, when I wherein the ligand is a substituted 8-hydroxy quinoline, ligand II, III are when the benzene ring, the preferred compound i-26-i-35 is structured as follows:

结构通式为ii的化合物,当其中配体I为取代的为4-羟基-1,5-萘啶,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物ii-1-ii-2结构如下所示: Compound of general structural formula ii, when I wherein the ligand is a substituted 4-hydroxy-1,5-naphthyridine, ligand II, III a benzene ring, a naphthalene ring or a phenanthrene ring and the like and substituted fused ring respectively when derivatives, preferably compounds ii-1-ii-2 structure is shown below: 结构通式为iii的化合物,当其中配体I为5-羟基-喹喔啉,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物iii-1-iii-3结构如下所示: A compound of the general structural formula iii, wherein when the ligand is 5-hydroxy-I - when quinoxaline, ligand II, III, respectively, a benzene ring, a naphthalene ring or a phenanthrene ring, condensed ring and substituted derivatives thereof, preferably compound iii-1-iii-3 structure is shown below: 结构通式为iv的化合物,当其中配体I为取代的2-(2-羟基苯基)苯并噁唑及其衍生物,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物iv-1-iv-5结构如下所示: Compound of general structural formula iv, when I wherein the ligand is a substituted 2- (2-hydroxyphenyl) benzoxazole and derivatives thereof, ligand II, III, respectively, a benzene ring, a naphthalene ring or phenanthrene ring and the like when a fused ring and substituted derivatives thereof, preferably compound iv-1-iv-5 structure is as follows:

结构通式为v的化合物,当其中配体I为取代的2-(2-羟基苯基)苯并咪唑及其衍生物,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物v-1-v-12结构如下所示: Compound of general structural formula v, wherein when the ligand I is a substituted 2- (2-hydroxyphenyl) benzoimidazole and derivatives thereof, ligand II, III, respectively, a benzene ring, a naphthalene ring or a phenanthrene ring fused when the ring and substituted derivatives thereof, preferably the compound v-1-v-12 structure is as follows:

结构通式为vi的化合物,当其中配体I为取代的2-(2-羟基苯基)苯并噻唑及其衍生物,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物vi-1-vi-6结构如下所示: A compound of the general structural formula vi, and when I wherein the ligand is a substituted 2- (2-hydroxyphenyl) benzothiazole and derivatives thereof, ligand II, III, respectively, a benzene ring, a naphthalene ring or a phenanthrene ring fused when the ring and substituted derivatives thereof, preferably compound vi-1-vi-6 structure is as follows: 结构通式为vii的化合物,当其中配体I为10-羟基苯并喹啉,配体II、III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物vii-1-vii-2结构如下所示: Compound of general structural formula vii, when I wherein the ligand is a 10-hydroxybenzo quinoline, ligand II, III, respectively, when a benzene ring, a naphthalene ring or a phenanthrene ring, condensed ring and substituted derivatives thereof, preferably compound vii-1-vii-2 structure is shown below:

结构通式为viii的化合物,当其中的配体I为吡啶-2-甲酸,配体II,III分别为苯环、萘环或菲环等稠环及其取代的衍生物时,优选的化合物viii-1结构如下所示: Viii structural formula of a compound, wherein when the ligand is a pyridine-2-carboxylic acid I, ligand II, III, respectively, a benzene ring, a naphthalene ring or a phenanthrene ring and the like and substituted derivatives thereof fused ring, preferred compounds viii-1 structure is shown below: 本发明使用Ga替代已有技术中的金属配合物的中心金属离子Al,从而为配体的选择提供了更大的自由度,以便开发出含有更多类型的配体的金属配合物,这样进一步扩展了可用于制备有机电致发光器件的有机化合物的种类。 The present invention is the use of Ga instead of the metal complex prior art central metal ion Al composition, thereby providing greater freedom in the choice of ligand is to develop a metal complex containing a ligand more types, which further extended type organic compound may be used to prepare the organic electroluminescent device.

本发明的中的材料具有以下优点:玻璃化温度高,热稳定性好,容易形成良好的无定形薄膜,该材料在溶液和固体膜中都有较强的荧光,荧光量子效率高。 The material of the invention has the following advantages: high glass transition temperature, good thermal stability, good easy to form an amorphous thin film, the material in the solution and the solid film has strong fluorescence, a high fluorescence quantum efficiency.

实验发现,含有三齿配体的络合物是一类稳定性极高的有机金属配合物,同时它们大多不易结晶,易于形成无定性薄膜。 It was found that complexes containing tridentate ligands are a class of highly stable organic metal complexes while they are most susceptible to crystallization, a thin film is easily formed without characterization. 对于制备电致发光器件十分有力。 For the preparation of an electroluminescent device is very powerful. 它们拥有较高的玻璃化转变温度,其中优选的(8-羟基喹啉)-(水杨醛缩邻苯胺苯酚)合镓(III)(化合物i)的玻璃化转变温度达到了477K,比目前公认的最好的发光材料Alq3的玻璃化温度448K高出30K。 They have a high glass transition temperature, wherein preferably the (8-hydroxyquinoline) - (salicylaldehyde phenol aniline o) gallium (III) (compound i) a glass transition temperature reaches 477K, than the current recognized the glass transition temperature is preferably higher than the light emitting material of Alq3 448K 30K.

本发明的有机电致发光材料具有优先传输电子、阻挡空穴,并且同时还可以用作发光体,包括单独成发光层,或者作为本体掺杂染料发光,或者作为掺杂的染料而发光。 The present invention has an organic electroluminescent material having preferentially transporting electrons, blocking holes, and also can be used as a light emitting body, including a light emitting layer into the individual, or as a dye-doped light emitting body or a dye as a dopant to emit light. 作为发光材料,其荧光的强度的荧光量子效率是衡量其发光特性的重要指标。 As a luminescent material, the fluorescence quantum efficiency of fluorescence intensity is an important measure of its luminescent characteristics. 实验发现本发明的有机电致发光材料在溶液和固体膜状态下均有很强的荧光。 It was found that there were strong fluorescence organic electroluminescent material in a solution state and a solid film of the present invention. 其中优选的(8-羟基喹啉)-(水杨醛缩邻苯胺苯酚)合镓(III)(化合物i)在二甲基甲酰胺溶液中的荧光量子效率为0.318,比同样条件下的Alq3的荧光量子效率(0.116)高出了1.74倍。 Among the preferred (8-hydroxyquinoline) - (salicylaldehyde phenol aniline o) gallium (III) (i) a compound fluorescence quantum efficiency in dimethyl formamide solution was 0.318, under the same conditions than Alq3 the fluorescence quantum efficiency (0.116) higher than 1.74 times. 该类材料属于配体发光的金属配合物,随着配体的改变,其配合物的发光也会相应的有所移动,可以实现从绿光到红光的发射。 Such materials luminescent ligand-metal complex, with the change of the ligand, luminescent complexes thereof will be a corresponding movement of the emission from green to red can be realized.

利用本发明的发光材料制备的有机电致发光器件可表现出高亮度、高效率的优越性能。 Prepared by the present invention has a light-emitting material for an organic electroluminescent device can exhibit high brightness, high efficiency superior performance. 经实验证实,无论是将本发明的材料单独作为发光层制备的有机电致发光器件,还是将本发明材料作为本体材料,搀杂染料制备的有机电致发光器件都具有很高的发光亮度和发光效率,如将本发明材料作为本体材料,搀杂如4-4-二氰基亚甲基-2-甲基-6-二甲氨基苯乙烯基-4H-吡喃(DCM)系列的红光染料即可实现饱和的红光发射。 Confirmed by experiments, either the material of the present invention is prepared as having a single light emitting layer of the organic electroluminescent device, or the material of the present invention as a bulk material, prepared dye doped organic electroluminescent device has high luminance and emission efficiency, such as the material of the present invention as a bulk material, such as doped 4-4- dicyanomethylene-2-methyl-6-dimethylamino-styryl -4H- pyran (DCM) dye red series saturated red emission can be realized.

附图说明 BRIEF DESCRIPTION

:图1为本发明制备的化合物i-1的质谱图。 : Preparation of the compound of the present invention, FIG. 1 i-1 of the spectrum.

图2为本发明制备的化合物i-2的质谱图。 FIG 2 is the preparation of compounds of the present invention the mass spectrum i-2.

图3为本发明制备的化合物iv-1的质谱图。 3 spectrum iv-1 Preparation of the compound of the present invention.

图4为本发明制备的化合物i-1在DMF溶液中的吸收光谱(a)和荧光发射谱(b)(激发波长为390nm)。 Preparation of compounds of the present invention, FIG. 4 i-1 in DMF absorption spectrum (a) Fluorescence emission spectra and (b) (excitation wavelength of 390nm).

图5为利用本发明化合物i-1制备的器件TTO/NPB(40nm)/i-1(40nm)/Mg∶Ag(10∶1)的电流-电压曲线(a)和亮度-电压曲线(b)。 FIG 5 is a compound of the present invention was prepared using i-1 device TTO / NPB (40nm) / i-1 (40nm) / Mg:Ag (10:1) current - voltage curves (a) and brightness - voltage curve (b ).

图6为利用本发明化合物i-1制备的器件TTO/NPB(40nm)/i-1(40nm)/Mg∶Ag(10∶1)的电致发光光谱图。 FIG 6 is a compound of the present invention was prepared using i-1 device TTO / NPB electrically (40nm) / i-1 (40nm) / Mg:Ag (10:1) electroluminescent spectrum of FIG.

图7为利用本发明化合物i-1制备的红光器件TTO/NPB(30nm)/i-1:DCJTB(2%,40nm)/Mg∶Ag(10∶1)的电致发光光谱图。 FIG 7 is a compound of the invention was prepared using i-1 red device TTO / NPB (30nm) / i-1: Electric DCJTB (2%, 40nm) / Mg:Ag (10:1) electroluminescent spectrum of FIG.

具体实施方式 Detailed ways

:以下介绍本发明的实施方式。 : The following describes the embodiments of the present invention.

化合物样品制备的实施方式:本发明的有机电致发光材料,采用在有机溶剂中合成的方法制备。 Sample preparation of compounds of the embodiment: The present invention is an organic electroluminescent material, a preparation method of synthesis in an organic solvent employed. 采用的步骤包括两部分:一是相应的三齿配体的合成,二是目标配合物的合成。 The step of using comprises two parts: First, the synthesis of the corresponding tridentate ligands, and second, the target complex was synthesized.

其中第一步的相关的三齿配体的合成采用希弗碱(Schiff base)的合成方法。 Wherein the first step of the synthesis of related tridentate ligands using Schiffer base (Schiff base) synthesis method. 具体过程是将含有计量比的邻羟基的芳香醛与含有邻羟基的芳香胺固相直接混合加热反应,或者在醇溶剂中加热回流反应,均可得到相应希弗碱的粗产品。 The specific process is an aromatic o-hydroxy aldehyde with a stoichiometric ratio of an aromatic amine containing a hydroxyl group ortho solid phase direct heating of the reaction mixture, or in an alcohol solvent was heated to reflux, to give the corresponding Schiff base can be a crude product. 然后通过在有机溶剂中重结晶的方法,很容易得到纯度很高的产品。 Then by recrystallization in an organic solvent, it is easy to obtain high purity products.

第二步的目标化合物的合成采用金属镓的无机盐和相应的配体在醇和水的体系中,通过加入碱控制产物的生成。 The second step of the synthesis of target compounds of gallium metal salts and corresponding ligand system of alcohol and water, by the addition of base to form the control product. 粗产品经过分区升华的方法提纯即可得高纯得产品。 The crude product was partitioned sublimation method of purification, to obtain high purity the products.

实施例1:化合物i-1的合成配体水杨醛缩邻氨基苯酚的合成:称取水杨醛1.22克(0.01摩尔)放入反应瓶,加入等摩尔的邻氨基苯酚1.09克(0.01摩尔),直接加热,即有红色物质产生,等反应完成后,使用乙醇重结晶即可得到针状的产品,即水杨醛缩邻氨基苯酚,产率为85%。 Example 1: Synthesis of compound i-1 ligand salicylaldehyde-o-aminophenol: said water salicylaldehyde 1.22 g (0.01 mol) was placed in a reaction flask, was added an equimolar amount of o-aminophenol 1.09 g (0.01 mol) , direct heating, i.e. red substances, etc. after completion of the reaction, and recrystallized from ethanol to obtain acicular product, i.e. salicylaldehyde o-aminophenol, 85% yield.

化合物i-1的合成:在装有搅拌装置的三口烧瓶中,加入20毫升0.88克(0.005摩尔)无水三氯化镓的乙醇溶液。 Synthesis of compound i-1: three-necked flask equipped with a stirring device, 20 ml of 0.88 g (0.005 mol) of anhydrous ethanol was three gallium chloride. 将0.73克(0.005摩尔)8-羟基喹啉完全溶解于20ml乙醇和0.43克(0.005摩尔)六氢吡啶的混合溶液,将此溶液在搅拌下慢慢滴入上述的溶液中,加完后继续搅拌5分钟。 0.73 g (0.005 mol) of 8-hydroxyquinoline was dissolved completely in 20ml of ethanol and 0.43 g (0.005 mol) of a mixed solution of piperidine, this solution was slowly added dropwise under stirring the above solution. After the addition continued stirred for 5 minutes. 将1.065克(0.005摩尔)水杨醛缩邻氨基苯酚完全溶解于100ml乙醇和0.85克(0.01摩尔)六氢吡啶的混合溶液,将此溶液在搅拌下慢慢滴加入上述的反应溶液中,加完后继续搅拌1个小时,然后与暗处放置陈化。 The 1.065 g (0.005 mole) of salicylaldehyde o-aminophenol was completely dissolved in 100ml of ethanol, and 0.85 g (0.01 mol) of a mixed solution of piperidine, the solution was slowly added dropwise with stirring at the above reaction solution was added after the stirring was continued for 1 hour, and then placed in the dark aging. 最后将此溶液加入与其等体积的去离子水,立即有大量的絮状沉淀产生,放入冰箱陈化10个小时,抽滤出固体,红外灯下干燥即得粗产品,产率为85%。 Finally, thereto was added an equal volume of deionized water, this immediate large flocculent precipitate in the refrigerator aged for 10 hours, the solid was filtered off with suction, and dried under an infrared lamp to obtain a crude product, 85% yield . 再经过分区升华提纯得到亮橙色得固体,即(8-羟基喹啉)-(水杨醛缩邻苯胺苯酚)合镓(III)(化合物i-1)纯品。 After sublimation purification to obtain the partition and then a bright orange solid was obtained, i.e., (8-quinolinolato) - (ortho aniline phenol salicylaldehyde) gallium (III) (compound i-1) pure product.

元素分析结果是:C 62.28%,H 3.52%,N 6.52%,O 11.53%;与理论值C 62.13%,H 3.51%,N 6.52%,O 11.53%吻合很好。 Elemental analysis is: C 62.28%, H 3.52%, N 6.52%, O 11.53%; theoretical value C 62.13%, H 3.51%, N 6.52%, O 11.53% in good agreement. 质谱测定分子量为M+=425,参见附图1。 Mass spectroscopy molecular weight M + = 425, see figure 1. 另外将其配制成10-5mol/L的DMF溶液,测定紫外可见吸收和荧光发射光谱,请参见附图4。 Further formulated into 10-5mol / L in DMF, measured ultraviolet-visible absorption and fluorescence emission spectra, see Figure 4. DSC测试可得其玻璃化转变温度为204℃。 DSC measurements may be obtaining a glass transition temperature of 204 ℃.

实施例2:化合物i-2的合成按照化合物i-1的方法合成,其中的三齿配体采用配体2-羟基-1-萘甲醛缩邻氨基苯酚的合成即可。 Example 2: Synthesis of compound i-2 i-1 is synthesized according to the method of the compound, wherein the ligand is tridentate ligands can be synthesized using 2-hydroxy-1-naphthaldehyde-o-aminophenol. 产物分区升华后得到纯品的质谱分析图请参见附图2。 Pure product was obtained after sublimation partition mass spectrometry see reference 2 in FIG. 质谱:m/e,475;元素分析:实验测定C:65.60%,H:3.49%N:5.80%;理论值:C:65.68%,H:3.58%,N:5.89% Mass spectrum: m / e, 475; Elemental analysis: experimental determination of C: 65.60%, H: 3.49% N: 5.80%; theoretical value: C: 65.68%, H: 3.58%, N: 5.89%

实施例3:化合物i-6的合成:按照化合物i-1的方法合成,其中的三齿配体采用邻羟基苯甲醛缩2-羟基-1-萘胺即可。 Example 3: Synthesis of compound i-6: Synthesis of compounds according to the i-1, wherein the tridentate ligand using salicylaldehyde condensation of 2-hydroxy-1-naphthylamine can. 质谱:m/e,475;元素分析:实验测定(%)C:65.61,H:3.52,N:5.92;理论值(%):C:65.68,H:3.58,N:5.89。 Mass spectrum: m / e, 475; Elemental analysis: experimental determination (%) C: 65.61, H: 3.52, N: 5.92; Theoretical value (%): C: 65.68, H: 3.58, N: 5.89.

实施例4:化合物i-8的合成按照化合物i-1的方法合成,其中的三齿配体采用2-羟基-1-萘甲醛缩3-羟基-2-萘胺即可。 Example 4: Synthesis of compound i-8 was synthesized according to the method of compound i-1, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde 3-hydroxy-2-naphthylamine can. 质谱:m/e,525;元素分析:实验测定C:68.50,H:3.59,N:5.30;理论值:C:68.57,H:3.62,N:5.33。 Mass spectrum: m / e, 525; Elemental analysis: experimental determination of C: 68.50, H: 3.59, N: 5.30; Theory: C: 68.57, H: 3.62, N: 5.33.

实施例5:化合物i-9的合成按照化合物i-1的方法合成,其中的三齿配体采用2-羟基-1-萘甲醛缩2-羟基-1-萘胺即可。 Example 5: Synthesis of compound i-9 is synthesized according to the method of compound i-1, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde 2-hydroxy-1-naphthylamine can. 质谱:m/e,525;元素分析:实验测定C:68.51,H:3.58,N:5.25;理论值:C:68.57,H:3.62,N:5.33。 Mass spectrum: m / e, 525; Elemental analysis: experimental determination of C: 68.51, H: 3.58, N: 5.25; Theory: C: 68.57, H: 3.62, N: 5.33.

实施例6:化合物i-19的合成按照化合物i-1的方法合成,其中的三齿配体采用3-羟基-2-萘甲醛缩3-羟基-2-萘胺即可。 Example 6: i-19 synthesis of the compounds synthesized according to the method of compound i-1, wherein the tridentate ligands using 3-hydroxy-2-naphthaldehyde to 3-hydroxy-2-naphthylamine. 质谱:m/e,525;元素分析:实验测定C:68.53,H:3.59,N:5.35;理论值:C:68.57,H:3.62,N:5.33。 Mass spectrum: m / e, 525; Elemental analysis: experimental determination of C: 68.53, H: 3.59, N: 5.35; Theory: C: 68.57, H: 3.62, N: 5.33.

实施例7:化合物i-26的合成按照化合物i-1的方法合成,采用5-氟-8-羟基喹啉替换8-羟基喹啉即可。 Example 7: Synthesis of compound i-26 i-1 according to the method of synthesis of the compounds, using 5-fluoro-8-hydroxyquinoline 8-hydroxyquinoline can be replaced. 质谱:m/e,443;元素分析:实验测定C:59.52,H:4.32,N:6.30;理论值:C:5959,H:4.29,N:6.32。 Mass spectrum: m / e, 443; Elemental analysis: experimental determination of C: 59.52, H: 4.32, N: 6.30; Theory: C: 5959, H: 4.29, N: 6.32.

实施例8:化合物i-27的合成按照化合物i-1的方法合成,采用5-氯-8-羟基喹啉替换8-羟基喹啉即可。 Example 8: Synthesis of compound i-27 i-1 according to the method of synthesis of the compounds, using 5-chloro-8-hydroxyquinoline 8-hydroxyquinoline can be replaced. 质谱:m/e,459.5;元素分析:实验测定C:57.40,H:4.20,N:6.01;理论值:C:57.45,H:4.13,N:6.09实施例9:化合物i-28的合成。 Mass spectrum: m / e, 459.5; Elemental analysis: experimental determination of C: 57.40, H: 4.20, N: 6.01; Theory: C: 57.45, H: 4.13, N: 6.09 Example 9: i-28 synthesis of the compounds.

按照化合物i-1的方法合成,采用5-氰基-8-羟基喹啉替换8-羟基喹啉即可。 I-1 according to the method of synthesizing a compound using 5-cyano-8-hydroxyquinoline 8-hydroxyquinoline can be replaced. 质谱:m/e,450;元素分析:实验测定C:61.30,H:4.15,N:9.25;理论值:C:61.33,H:4.22,N:9.33。 Mass spectrum: m / e, 450; Elemental analysis: experimental determination of C: 61.30, H: 4.15, N: 9.25; Theory: C: 61.33, H: 4.22, N: 9.33.

实施例10:化合物i-32的合成按照化合物i-1的方法合成,采用5,6,7-三氟-8-羟基喹啉替换8-羟基喹啉即可。 Example 10: Synthesis of compound i-32 i-1 according to the method of synthesis of the compounds, using 5,6,7-trifluoro-8-hydroxyquinoline 8-hydroxyquinoline can be replaced. 质谱:m/e,479;元素分析:实验测定C:55.09,H:2.49,N:5.81;理论值:C:55.11,H:2.51,N:5.85。 Mass spectrum: m / e, 479; Elemental analysis: experimental determination of C: 55.09, H: 2.49, N: 5.81; Theory: C: 55.11, H: 2.51, N: 5.85.

实施例11:化合物i-34的合成。 Synthesis of compound i-34: The Example 11.

按照化合物i-1的方法合成,采用5-氯-8-羟基喹啉替换8-羟基喹啉,其中三齿配体采用2-羟基-1-萘甲醛缩3-羟基-2-萘胺即可。 I-1 according to the method of synthesis of compounds, using 5-chloro-8-hydroxyquinoline 8-hydroxyquinoline Alternatively, where tridentate ligand from 2-hydroxy-1-naphthaldehyde 3-hydroxy-2-naphthylamine i.e. can. 质谱:m/e,509.5;元素分析:实验测定C:61.23,H:3.15,N:5.52;理论值:C:61.24,H:3.14,N:5.50实施例12:化合物i-35的合成。 Mass spectrum: m / e, 509.5; Elemental analysis: experimental determination of C: 61.23, H: 3.15, N: 5.52; Theory: C: 61.24, H: 3.14, N: 5.50 Example 12: Compound i-35 synthesis.

按照化合物i-1的方法合成,采用5-氟-8-羟基喹啉替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩2-羟基-1-萘胺即可。 I-1 according to the method of synthesis of compounds, using 5-fluoro-8-hydroxyquinoline 8-hydroxyquinoline Alternatively, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde 2-hydroxy-1-naphthylamine It can be. 质谱:543;元素分析:实验测定C:66.29,H:3.31,N:5.15;理论值:C:66.30,H:3.32,N:5.16。 Mass spectrum: 543; Elemental analysis: experimental determination of C: 66.29, H: 3.31, N: 5.15; Theory: C: 66.30, H: 3.32, N: 5.16.

实施例13:化合物ii-1的合成按照化合物i-1的方法合成,采用4-羟基-1,5-萘啶替换8-羟基喹啉即可。 Example 13: ii-1 Synthesis of compound i-1 in accordance with the method of synthesis of compounds using 4-hydroxy-1,5-naphthyridin-8-hydroxyquinoline can be replaced. 质谱:m/e,426;元素分析:实验测定C:59.10,H:3.20,N:9.81;理论值:C:59.15,H:3.29,N:9.86。 Mass spectrum: m / e, 426; Elemental analysis: experimental determination of C: 59.10, H: 3.20, N: 9.81; Theory: C: 59.15, H: 3.29, N: 9.86.

实施例14:化合物ii-2的合成。 Synthesis of compound ii-2: the Example 14.

按照化合物i-1的方法合成,采用4-羟基-1,5-萘啶替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩邻羟基苯胺即可。 I-1 according to the method of synthesis of compounds using 4-hydroxy-1,5-naphthyridin-8-hydroxyquinoline Alternatively, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde can be ortho-hydroxyaniline. 质谱:m/e,476元素分析:实验测定C:63.01,H:3.35,N:8.79;理论值:C:63.03,H:3.36,N:8.82。 Mass spectrum: m / e, 476 Elemental analysis: experimental determination of C: 63.01, H: 3.35, N: 8.79; Theory: C: 63.03, H: 3.36, N: 8.82.

实施例15:化合物iii-1的合成按照化合物i-1的方法合成,采用5-羟基-喹喔啉替换8-羟基喹啉即可。 Example 15: iii-1 Synthesis of compound i-1 in accordance with the method of compound synthesis, using 5-hydroxy - quinoxaline 8-hydroxyquinoline can be replaced. 质谱:m/e,426;元素分析:实验测定C:59.11,H:3.21,N:9.79;理论值:C:59.15,H:3.29,N:9.86。 Mass spectrum: m / e, 426; Elemental analysis: experimental determination of C: 59.11, H: 3.21, N: 9.79; Theory: C: 59.15, H: 3.29, N: 9.86.

实施例16:化合物iii-2的合成按照化合物i-1的方法合成,采用5-羟基-喹喔啉替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩邻羟基苯胺即可。 Example 16: Synthesis of Compound iii-2 i-1 according to the method of synthesis of the compounds, using 5-hydroxy - quinoxaline replacing 8-hydroxyquinoline, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde to o-hydroxyaniline. 质谱:m/e,476;元素分析:实验测定C:63.00,H:3.33,N:8.75;理论值:C:63.03,H:3.36,N:8.82。 Mass spectrum: m / e, 476; Elemental analysis: experimental determination of C: 63.00, H: 3.33, N: 8.75; Theory: C: 63.03, H: 3.36, N: 8.82.

实施例17:化合物iii-3的合成按照化合物i-1的方法合成,采用5-羟基-喹喔啉替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩3-羟基-2-萘胺即可。 Example 17: Synthesis of Compound iii-3 i-1 according to the method of synthesizing a compound using 5-hydroxy - quinoxaline replacing 8-hydroxyquinoline, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde to 3-hydroxy-2-naphthylamine. 质谱:m/e,526;元素分析:实验测定C:66.12,H:3.39,N:7.91;理论值:C:66.16,H:3.42,N:7.99。 Mass spectrum: m / e, 526; Elemental analysis: experimental determination of C: 66.12, H: 3.39, N: 7.91; Theory: C: 66.16, H: 3.42, N: 7.99.

实施例18:化合物iv-1的合成按照化合物i-1的方法合成,采用2-(2-羟基苯基)苯并噁唑替换8-羟基喹啉即可。 Example 18: iv-1 Synthesis of compound i-1 in accordance with the method of synthesis of the compounds, 2- (2-hydroxyphenyl) benzoxazole-8-hydroxyquinoline can be replaced. 其质谱图参见附图6。 Mass spectrum see Figure 6 FIG. 质谱:m/e,491;元素分析:实验测定C:63.39,H:3.40,N:5.62;理论值:C:63.41,H:3.46,N:5.69。 Mass spectrum: m / e, 491; Elemental analysis: experimental determination of C: 63.39, H: 3.40, N: 5.62; Theory: C: 63.41, H: 3.46, N: 5.69.

实施例19:化合物iv-2的合成按照化合物i-1的方法合成,采用2-(2-羟基苯基)苯并噁唑替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩邻羟基苯胺。 Example 19: Synthesis of Compound iv-2 i-1 according to the method of synthesis of the compounds, 2- (2-hydroxyphenyl) benzoxazole replacing 8-hydroxyquinoline, wherein the tridentate ligand using 2-hydroxy 1-naphthaldehyde o - hydroxyaniline. 质谱:m/e,541;元素分析:实验测定C:66.50,H:3.49,N:5.15;理论值:C:66.54,H:3.51,N:5.18实施例20:化合物iv-3的合成按照化合物i-1的方法合成,采用2-(2-羟基-3,5-二氟取代的苯基)苯并噁唑替换8-羟基喹啉即可。 Mass spectrum: m / e, 541; Elemental analysis: experimental determination of C: 66.50, H: 3.49, N: 5.15; Theory: C: 66.54, H: 3.51, N: 5.18 Example 20: Compound iv-3 synthesized according to i-1 compound synthesized using 2- (2-hydroxy-3,5-fluoro-substituted phenyl) benzoxazole 8-hydroxyquinoline can be replaced. 质谱:m/e,527;元素分析:实验测定C:59.15,H:2.84,N:5.29;理论值:C:59.20,H:2.85,N:5.31实施例21:化合物iv-4的合成按照化合物i-1的方法合成,采用2-(2-羟基-4,6-二氟取代的苯基)苯并噁唑替换8-羟基喹啉即可。 Mass spectrum: m / e, 527; Elemental analysis: experimental determination of C: 59.15, H: 2.84, N: 5.29; Theory: C: 59.20, H: 2.85, N: 21 5.31 Example: Synthesis of Compound iv-4 according i-1 compound synthesized from 2- (2-hydroxy-4,6-fluoro-substituted phenyl) benzoxazole 8-hydroxyquinoline can be replaced. 质谱:m/e,527;元素分析:实验测定C:59.16,H:2.83,N:5.31;理论值:C:59.20,H:2.85,N:5.31。 Mass spectrum: m / e, 527; Elemental analysis: experimental determination of C: 59.16, H: 2.83, N: 5.31; Theory: C: 59.20, H: 2.85, N: 5.31.

实施例22:化合物iv-5的合成按照化合物i-1的方法合成,采用2-(2-羟基-3,4,5-三氟取代的苯基)苯并噁唑替换8-羟基喹啉即可。 Example 22: Synthesis of Compound iv-5 i-1 according to the method of synthesis of the compounds, 2- (2-hydroxy-3,4,5-trifluoro-substituted phenyl) benzoxazole replacing 8-hydroxyquinoline It can be. 质谱:m/e,545;元素分析:实验测定C:57.19,H:2.45,N:5.10;理论值:C:57.25,H:2.57,N:5.14。 Mass spectrum: m / e, 545; Elemental analysis: experimental determination of C: 57.19, H: 2.45, N: 5.10; Theory: C: 57.25, H: 2.57, N: 5.14.

实施例23:化合物v-1的合成按照化合物i-1的方法合成,采用2-(2-羟基苯基)苯并咪唑替换8-羟基喹啉即可。 Example 23: v-1 Synthesis of compound i-1 in accordance with the method of synthesis of the compounds, 2- (2-hydroxyphenyl) benzimidazole-8-hydroxyquinoline can be replaced. 质谱:m/e,490;元素分析:实验测定C:63.65,H:3.65,N:8.52;理论值:C:63.67,H:3.67,N:8.57。 Mass spectrum: m / e, 490; Elemental analysis: experimental determination of C: 63.65, H: 3.65, N: 8.52; Theory: C: 63.67, H: 3.67, N: 8.57.

实施例24:化合物v-2的合成按照化合物i-1的方法合成,采用1-甲基-2-(2-羟基苯基)苯并咪唑替换8-羟基喹啉即可。 Example 24: Synthesis of Compound v-2 i-1 according to the method of synthesis of the compounds, using 1-methyl-2- (2-hydroxyphenyl) benzimidazole-8-hydroxyquinoline can be replaced. 质谱:m/e,504;元素分析:实验测定C:64.25,H:3.90,N:8.30;理论值:C:64.29,H:3.97,N:8.33。 Mass spectrum: m / e, 504; Elemental analysis: experimental determination of C: 64.25, H: 3.90, N: 8.30; Theory: C: 64.29, H: 3.97, N: 8.33.

实施例25:化合物v-3的合成按照化合物i-1的方法合成,采用1-苯基-2-(2-羟基苯基)苯并咪唑替换8-羟基喹啉即可。 Example 25: Synthesis of Compound v-3 i-1 according to the method of synthesis of the compounds, using 1-phenyl-2- (2-hydroxyphenyl) benzimidazole-8-hydroxyquinoline can be replaced. 质谱:m/e,568;元素分析:实验测定C:67.59,H:4.02,N:7.35;理论值:C:67.61,H:4.05,N:7.39。 Mass spectrum: m / e, 568; Elemental analysis: experimental determination of C: 67.59, H: 4.02, N: 7.35; Theory: C: 67.61, H: 4.05, N: 7.39.

实施例26:化合物v-4的合成按照化合物i-1的方法合成,采用2-(2-羟基苯基)苯并咪唑替换8-羟基喹啉。 Example 26: Synthesis of Compound v-4 i-1 according to the method of synthesizing a compound, 2- (2-hydroxyphenyl) benzimidazole replacing 8-hydroxyquinoline. 其中三齿配体采用2-羟基-1-萘甲醛缩邻羟基苯胺即可。 Wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde can be ortho-hydroxyaniline. 质谱:m/e,540;元素分析:实验测定C66.60,:H:3.72,N:7.80;理论值:C:66.67,H:3.70,N:7.78实施例27:化合物v-6合成按照化合物i-1的方法合成,采用1-苯基-2-(2-羟基苯基)苯并咪唑替换8-羟基喹啉,其中的三齿配体采用配体2-羟基-1-萘甲醛缩邻氨基苯酚的合成即可。 Mass spectrum: m / e, 540; Elemental analysis: experimental determination C66.60,: H: 3.72, N: 7.80; Theory: C: 66.67, H: 3.70, N: 7.78 Example 27: Synthesis of Compound v-6 according to i-1 compound synthesized using 1-phenyl-2- (2-hydroxyphenyl) benzimidazole-8-hydroxyquinoline Alternatively, the tridentate ligand wherein the ligand using 2-hydroxy-1-naphthaldehyde condensation of o-aminophenol can be synthesized. 质谱:m/e,617;元素分析:实验测定C:69.99,H:4.02,N:6.78;理论值:C:70.01,H:4.05,N:6.81。 Mass spectrum: m / e, 617; Elemental analysis: experimental determination of C: 69.99, H: 4.02, N: 6.78; Theory: C: 70.01, H: 4.05, N: 6.81.

实施例28:化合物v-7的合成按照化合物i-1的方法合成,采用1-甲基-2-(2-羟基-3,5-二氟-苯基)苯并咪唑替换8-羟基喹啉即可。 Example 28: Synthesis of Compound v-7 i-1 according to the method of synthesis of the compounds, using 1-methyl-2- (2-hydroxy-3,5-difluoro-phenyl) - benzimidazole-8-hydroxyquinoline alternatively morpholine can be. 质谱:m/e,540;元素分析:实验测定C:59.98,H:3.30,N:7.81;理论值:C:60.00,H:3.33,N:7.78实施例29:化合物v-8的合成按照化合物i-1的方法合成,采用1-甲基-2-(2-羟基-4,6-二氟-苯基)苯并咪唑替换8-羟基喹啉即可。 Mass spectrum: m / e, 540; Elemental analysis: experimental determination of C: 59.98, H: 3.30, N: 7.81; Theory: C: 60.00, H: 3.33, N: 7.78 Example 29: Synthesis of Compound v-8 according to i-1 compound synthesized using 1-methyl-2- (2-hydroxy-4,6-difluoro-phenyl) - benzoimidazol-8-hydroxyquinoline can be replaced. 质谱:m/e,540;元素分析:实验测定C:59.97,H:3.28,N:7.75;理论值:C:60.00,H:3.33,N:7.78。 Mass spectrum: m / e, 540; Elemental analysis: experimental determination of C: 59.97, H: 3.28, N: 7.75; Theory: C: 60.00, H: 3.33, N: 7.78.

实施例30:化合物v-9合成按照化合物i-1的方法合成,采用2-(2-羟基-3,4,5,6-四氟-苯基)苯并咪唑替换8-羟基喹啉即可。 Example 30: Synthesis of compound v-9 i-1 according to the method of synthesizing a compound, 2- (2-hydroxy-3,4,5,6-tetrafluoro - phenyl) benzimidazole Alternatively i.e. 8-hydroxyquinoline can. 质谱:m/e,562;元素分析:实验测定C:55.50,H:2.47,N:7.45;理论值:C:55.52,H:2.49,N:7.47实施例31:化合物v-10的合成按照化合物i-1的方法合成,采用1-甲基-2-(2-羟基-3,4,5,6-四氟-苯基)苯并咪唑替换8-羟基喹啉即可。 Mass spectrum: m / e, 562; Elemental analysis: experimental determination of C: 55.50, H: 2.47, N: 7.45; Theory: C: 55.52, H: 2.49, N: 7.47 Example 31: Synthesis of compound v-10 in accordance with the i-1 compound synthesized using 1-methyl-2- (2-hydroxy-3,4,5,6-tetrafluoro-phenyl) - benzoimidazol-8-hydroxyquinoline can be replaced. 质谱:m/e,576;元素分析:实验测定C:56.20,H:2.75,N:7.29;理论值:C:56.25,H:2.78,N:7.29实施例32:化合物v-11的合成按照化合物i-1的方法合成,采用2-(2-羟基-萘基)苯并咪唑替换8-羟基喹啉即可。 Mass spectrum: m / e, 576; Elemental analysis: experimental determination of C: 56.20, H: 2.75, N: 7.29; Theory: C: 56.25, H: 2.78, N: 7.29 Example 32: Synthesis of compound v-11 in accordance with the i-1 compound synthesized using 2- (2 - naphthyl) benzimidazole-8-hydroxyquinoline can be replaced. 质谱:m/e,540;元素分析:实验测定C:66.65,H:3.71,N:7.81;理论值:C:66.67,H:3.70,N:7.78。 Mass spectrum: m / e, 540; Elemental analysis: experimental determination of C: 66.65, H: 3.71, N: 7.81; Theory: C: 66.67, H: 3.70, N: 7.78.

实施例33:化合物v-12的合成按照化合物i-1的方法合成,采用1-甲基-2-(2-羟基-萘基)苯并咪唑替换8-羟基喹啉即可。 Example 33: Synthesis of compound v-12 i-1 according to the method of synthesis of the compounds, using 1-methyl-2- (2-hydroxy - naphthyl) benzimidazole-8-hydroxyquinoline can be replaced. 质谱:m/e,554;元素分析:实验测定C:67.14,H:3.98,N:7.55;理论值:C:67.15,H:3.97,N:7.58。 Mass spectrum: m / e, 554; Elemental analysis: experimental determination of C: 67.14, H: 3.98, N: 7.55; Theory: C: 67.15, H: 3.97, N: 7.58.

实施例34:化合物vi-1的合成按照化合物i-1的方法合成,采用2-(2-羟基-苯基)苯并噻唑替换8-羟基喹啉即可。 Example 34: vi-1 Synthesis of compound i-1 in accordance with the method of synthesizing a compound, 2- (2-hydroxy-phenyl) - 8-quinolinol replaced benzothiazole can. 质谱:m/e,507;元素分析:实验测定C:61.50,H:3.36,N:5.50;理论值:C:61.54,H:3.35,N:5.52。 Mass spectrum: m / e, 507; Elemental analysis: experimental determination of C: 61.50, H: 3.36, N: 5.50; Theory: C: 61.54, H: 3.35, N: 5.52.

实施例35:化合物vi-2的合成按照化合物i-1的方法合成,采用2-(2-羟基-苯基)苯并噻唑替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩邻羟基苯胺即可。 Example 35: Synthesis of Compound vi-2 i-1 according to the method of synthesis of the compounds, 2- (2-hydroxy-phenyl) - 8-quinolinol replaced benzothiazole, wherein the tridentate ligand using 2-hydroxy o - 1-naphthaldehyde can hydroxyaniline. 质谱:m/e,557;元素分析:实验测定C:64.61,H:34.10,N:5.01;理论值:C:64.63,H:34.11,N:5.03实施例36:化合物vi-3的合成按照化合物i-1的方法合成,采用2-(2-羟基-3,5-二氟-苯基)苯并噻唑替换8-羟基喹啉即可。 Mass spectrum: m / e, 557; Elemental analysis: experimental determination of C: 64.61, H: 34.10, N: 5.01; Theory: C: 64.63, H: 34.11, N: 5.03 Example 36: Synthesis of Compound vi-3 according to i-1 compound synthesized using 2- (2-hydroxy-3,5-difluoro-phenyl) - benzothiazol-8-hydroxyquinoline can be replaced. 质谱:m/e,543;元素分析:实验测定C:57.45,H:2.75,N:5.15;理论值:C:57.46,H:2.76,N:5.16。 Mass spectrum: m / e, 543; Elemental analysis: experimental determination of C: 57.45, H: 2.75, N: 5.15; Theory: C: 57.46, H: 2.76, N: 5.16.

实施例37:化合物vi-4的合成按照化合物i-1的方法合成,采用2-(2-羟基-4,6-二氟-苯基)苯并噻唑替换8-羟基喹啉即可。 Example 37: Synthesis of Compound vi-4 i-1 according to the method of synthesis of the compounds, 2- (2-hydroxy-4,6-difluoro-phenyl) - benzothiazol-8-hydroxyquinoline can be replaced. 质谱:m/e,543;元素分析:实验测定C:57.44,H:2.74,N:5.15;理论值:C:57.46,H:2.76,N:5.16。 Mass spectrum: m / e, 543; Elemental analysis: experimental determination of C: 57.44, H: 2.74, N: 5.15; Theory: C: 57.46, H: 2.76, N: 5.16.

实施例38:化合物vi-5的合成按照化合物i-1的方法合成,采用2-(2-羟基-3,4,5,6-四氟-苯基)苯并噻唑替换8-羟基喹啉即可。 Example 38: Synthesis of Compound vi-5 i-1 according to the method of synthesis of the compounds, 2- (2-hydroxy-3,4,5,6-tetrafluoro-phenyl) - benzothiazole replaced 8-hydroxyquinoline It can be. 质谱:m/e,579;元素分析:实验测定C:53.87,H:2.23,N:4.80;理论值:C:53.89,H:2.25,N:4.84。 Mass spectrum: m / e, 579; Elemental analysis: experimental determination of C: 53.87, H: 2.23, N: 4.80; Theory: C: 53.89, H: 2.25, N: 4.84.

实施例39:化合物vi-6的合成按照化合物i-1的方法合成,采用2-(2-羟基-萘基)苯并噻唑替换8-羟基喹啉即可。 Example 39: Synthesis of Compound vi-6 i-1 according to the method of synthesis of the compounds, 2- (2-hydroxy - naphthyl) 8-hydroxyquinoline can be replaced benzothiazole. 质谱:557;元素分析:实验测定C:64.62,H:34.09,N:5.01;理论值:C:64.63,H:34.11,N:5.03实施例40:化合物vii-1的合成按照化合物i-1的方法合成,采用10-羟基苯并喹啉替换8-羟基喹啉即可。 Mass spectrum: 557; Elemental analysis: experimental determination of C: 64.62, H: 34.09, N: 5.01; Theory: C: 64.63, H: 34.11, N: 5.03 Example 40: vii-1 Synthesis of compound according to compound i-1 the method of synthesis, using 10-hydroxybenzo quinoline-8-hydroxyquinoline can be replaced. 质谱:m/e,475;元素分析:实验测定C:65.67,H:3.55,N:5.87;理论值:C:65.68,H:3.58,N:5.89。 Mass spectrum: m / e, 475; Elemental analysis: experimental determination of C: 65.67, H: 3.55, N: 5.87; Theory: C: 65.68, H: 3.58, N: 5.89.

实施例41:化合物vii-2的合成按照化合物i-1的方法合成,采用10-羟基苯并喹啉替换8-羟基喹啉,其中的三齿配体采用2-羟基-1-萘甲醛缩邻羟基苯胺即可。 Example 41: Synthesis of Compound vii-2 i-1 according to the method of synthesis of the compounds, and use of 10-hydroxybenzo quinoline-8-hydroxyquinoline Alternatively, wherein the tridentate ligand from 2-hydroxy-1-naphthaldehyde to o-hydroxyaniline. 质谱:m/e,525;元素分析:实验测定C:68.49,H:3.57,N:5.26;理论值:C:68.57,H:3.62,N:5.33。 Mass spectrum: m / e, 525; Elemental analysis: experimental determination of C: 68.49, H: 3.57, N: 5.26; Theory: C: 68.57, H: 3.62, N: 5.33.

实施例42:化合物viii-1的合成按照化合物i-1的方法合成,采用吡啶-2-甲酸替换8-羟基喹啉即可。 Example 42: viii-1 Synthesis of compound according to the method of synthesis of compound i-1, using pyridine-2-carboxylic acid Alternatively to 8-quinolinol. 质谱:m/e,403;元素分析:实验测定C:56.59,H:3.24,N:6.94;理论值:C:56.58,H:3.23,N:6.95。 Mass spectrum: m / e, 403; Elemental analysis: experimental determination of C: 56.59, H: 3.24, N: 6.94; Theory: C: 56.58, H: 3.23, N: 6.95.

有机电致发光器件实施例:实施例43:采用化合物i-1单独作发光层材料,制备了电致发光器件,其结构为:ITO/NPB(40nm)/i-1(40nm)/Mg∶Ag在一个清洁过的氧化铟-氧化锡(ITO)覆盖的玻璃基片上,通过真空蒸发的方法依次连续蒸镀40nm的空穴传输材料N,N'-二苯基-N,N'-二(N-苯基-1-萘胺)-联苯二胺(NPB),40nm的发光材料本发明中的化合物i-1((8-羟基喹啉)-(水杨醛缩邻苯胺苯酚)合镓(III))和200nm的金属Mg∶Ag(10∶1)的合金作阴极。 The organic electroluminescent device of Example: Example 43: i-1 using the compound alone as a light emitting layer material, an electroluminescent device was prepared, having the structure: ITO / NPB (40nm) / i-1 (40nm) / Mg: Ag in a cleaned indium oxide - tin oxide on a glass substrate (ITO) covered by a vacuum evaporation method successively deposited 40nm of a hole transporting material N, N'- diphenyl -N, N'- two (N- phenyl-1-naphthylamine) - benzidine (NPB), the compound of the present invention, the light emitting material of 40nm i-1 ((8- quinolinolato) - (ortho aniline phenol salicylaldehyde) gallium (III)) and a metal 200nm Mg:Ag (10:1) alloy as the cathode. 该器件的性能测试结果如下:启亮电压为3.5V,最大发光波长为578nm,最大亮度为4400cd/m2(25V下)。 Performance test results of the device is as follows: Qiliang voltage is 3.5V, the maximum emission wavelength of 578nm, a maximum brightness of 4400cd / m2 (25V down). 其电流-电压曲线和亮度-电压曲线请参见附图5,电致发光光谱参见附图6。 Its current - voltage curve and brightness - voltage curves see figures 5, electroluminescence spectra see Figure 6.

实施例44:采用化合物i-1作本体材料,掺杂红光染料如DCJTB,制备红色电致发光器件,其器件结构为:ITO/NPB(40nm)/i-1:DCJTB(2%)(40nm)/Mg∶Ag。 Example 44: The compound i-1 as the body material, doped with a red dye such as DCJTB, electric red electroluminescent device was prepared, which device structure: ITO / NPB (40nm) / i-1: DCJTB (2%) ( 40nm) / Mg:Ag.

在一个清洁过的氧化铟-氧化锡(ITO)覆盖的玻璃基片上,通过真空蒸发的方法依次连续蒸镀30nm的空穴传输材料N,N'-二苯基-N,N'-二(N-苯基-1-萘胺)-联苯二胺(NPB),40nm的发光层为本发明中的化合物i-1和2%(质量百分比)的红光染料,和200nm的金属Mg∶Ag(10∶1)的合金作阴极。 In a cleaned indium oxide - tin oxide on a glass substrate (ITO) covered by a vacuum evaporation method is successively deposited a hole transport material 30nm N, N'- diphenyl -N, N'- bis ( N- phenyl-1-naphthylamine) - benzidine (of NPB), the present light-emitting layer 40nm i-1 and 2% (by mass percent) of red dye, and a metal compound 200nm invention Mg: Ag (10:1) alloy as the cathode. 该器件的性能测试结果如下:启亮电压为2.5V,发光中心波长为644nm,其色坐标为(0.67,0.33),为纯正的红光。 Performance test results of the device is as follows: Qiliang voltage of 2.5V, a center wavelength of 644nm emission, color coordinates of (0.67, 0.33), as pure red. 器件在24V时亮度为2980cd/m2,电致发光光谱请参见附图7。 When the brightness is 24V device 2980cd / m2, electroluminescence spectrum See Figure 7.

尽管结合优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解,所附权利要求概括了本发明的范围,在本发明构思的引导下,本领域的技术人员应意识到,对本发明的各实施例方案所进行的一定的改变,都将被本发明的权利要求书的精神和范围所覆盖。 While various embodiments of the present invention has been described, but the present invention is not limited to the above embodiments, it should be understood that the scope of the appended claims of the present invention is summarized in the guide concept of the present invention, those skilled in the art should appreciated that changes to certain embodiments of the present invention is carried out, according to the present invention will be claimed from the spirit and scope of the coverage requirements.

Claims (11)

1.一种有机电致发光材料,该材料是一种中心原子是镓原子的含有三齿配体的金属配合物,其特征在于,该发光材料具有以下结构: 1. An organic electroluminescent material, the material is gallium atom is a central atom of the metal-containing tridentate ligand complex, characterized in that the luminescent material has the following structure: 上述结构式中,I、II和III所在的配体分别代表芳香环或者杂环化合物及其取代的衍生物,其中I所在的两齿配体处的芳香环选自8-羟基喹啉、4-羟基-1,5-萘啶、5-羟基-喹喔啉、2-(2-羟基苯基)苯并噁唑、2-(2-羟基苯基)苯并咪唑、2-(2-羟基苯基)苯并噻唑、10-羟基苯并喹啉或吡啶-2-甲酸中的一种;II、III处的芳香环选自苯环、萘环、菲环、吡啶、噻唑或咔唑中的一种,其中I、II、III上可以有一个或多个取代基,取代基选自氢原子、烷基、异烷基、烷氧基、硝基、氰基、氨基、卤素原子、含有6-20个碳原子的芳香基、呋喃、噻吩、吡咯或吡啶中的一种。 In the above formulas, I, II and III where the ligands represent an aromatic ring or a heterocyclic compound and substituted derivatives thereof wherein the aromatic ring ligands at the two teeth where I is selected from 8-hydroxyquinoline, 4 hydroxy-1,5-naphthyridine, 5-hydroxy - quinoxaline, 2- (2-hydroxyphenyl) benzoxazole, 2- (2-hydroxyphenyl) benzimidazole, 2- (2-hydroxy phenyl) benzothiazole, or a 10-hydroxybenzo quinoline-2-carboxylic acid in one kind; II, an aromatic ring selected from a benzene at III, a naphthalene ring, a phenanthrene ring, a pyridine, thiazole or carbazole one in which the I, II, III may have one or more substituents, the substituents are selected from a hydrogen atom, an alkyl, isoalkyl, alkoxy, nitro, cyano, amino, a halogen atom, comprising aryl group of 6 to 20 carbon atoms, furan, thiophene, pyrrole or a pyridine.
2.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中所述的I所在的两齿配体为8-羟基喹啉,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, characterized in that the two bidentate ligands wherein where I is the 8-hydroxyquinoline, II, III, respectively, a benzene ring, a naphthalene ring, or a medium phenanthrene ring.
3.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中所述的I所在的两齿配体为取代的8-羟基喹啉,II和III均为苯环。 According to claim 1, one of the organic electroluminescent material, wherein said two bidentate ligands where I is a substituted 8-hydroxy quinoline, II and III are both benzene rings.
4.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中I所在的两齿配体为4-羟基-1,5-萘啶,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, wherein two bidentate ligand where I is 4-hydroxy-1,5-naphthyridine, II, III, respectively, a benzene ring, a naphthalene ring or a phenanthrene ring.
5.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中I所在的两齿配体为5-羟基-喹喔啉,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, wherein two bidentate ligand where I is 5-hydroxy - quinoxaline, II, III, respectively, a benzene ring, a naphthalene ring or phenanthrene in a cyclic.
6.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中I所在的两齿配体为2-(2-羟基苯基)苯并噁唑及其衍生物,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, wherein I where two bidentate ligand is 2- (2-hydroxyphenyl) benzoxazole and derivatives thereof, II, III respectively a benzene ring, a naphthalene ring or one of the phenanthrene ring.
7.根据权利要求1所述的一种有机电致发光材料,其特征在于,I所在的两齿配体为2-(2-羟基苯基)苯并咪唑及其衍生物,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, characterized in that, where two teeth of the I ligand is 2- (2-hydroxyphenyl) benzoimidazole and derivatives thereof, II, III, respectively It is a benzene ring, the naphthalene ring or phenanthrene ring one kind.
8.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中所述的I所在的两齿配体为2-(2-羟基苯基)苯并噻唑及其衍生物,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, wherein said two bidentate ligands where I is 2- (2-hydroxyphenyl) benzothiazole and derivatives thereof, II, III, respectively, a benzene ring, a naphthalene ring or one of the phenanthrene ring.
9.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中I所在的两齿配体为10-羟基苯并喹啉,II、III分别为苯环、萘环或菲环中的一种。 According to claim 1, one of the organic electroluminescent material, wherein two bidentate ligand where I is 10-hydroxybenzo quinoline, II, III, respectively, a benzene ring, a naphthalene ring or phenanthrene in a cyclic.
10.根据权利要求1所述的一种有机电致发光材料,其特征在于,其中I所在的两齿配体为吡啶-2-甲酸,II、III均为苯环。 According to claim 1, one of the organic electroluminescent material, wherein I where two bidentate ligands is pyridine-2-carboxylic acid, II, III are benzene rings.
11.权利要求1所述的一种有机电致发光材料的应用,其特征在于这种材料可用在由多层有机材料组成的有机电致发光器件中的载流子传输层或发光层,也可用作掺杂的染料或者作为红光染料的本体材料。 11. The one kind of claim 1 are applied in an organic electroluminescent material, wherein this material may be used in organic material has a multilayer organic carrier transporting layer or a light-emitting layer in electroluminescent devices, but also It may be used as a dye-doped bulk material or as a red dye.
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