CN102796133A - 一种稀土铕配合物及其作为发光材料的应用 - Google Patents
一种稀土铕配合物及其作为发光材料的应用 Download PDFInfo
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- CN102796133A CN102796133A CN2011101398421A CN201110139842A CN102796133A CN 102796133 A CN102796133 A CN 102796133A CN 2011101398421 A CN2011101398421 A CN 2011101398421A CN 201110139842 A CN201110139842 A CN 201110139842A CN 102796133 A CN102796133 A CN 102796133A
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 22
- 238000004020 luminiscence type Methods 0.000 title abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 45
- 230000007935 neutral effect Effects 0.000 claims abstract description 19
- -1 amino, N-substituted-amino Chemical group 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000003545 alkoxy group Chemical class 0.000 claims description 17
- 125000003368 amide group Chemical class 0.000 claims description 17
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- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000000304 alkynyl group Chemical group 0.000 claims description 11
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- 125000002252 acyl group Chemical class 0.000 claims description 9
- 125000004185 ester group Chemical class 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
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- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 7
- 125000005518 carboxamido group Chemical group 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- NSPLFNGUPLZYHV-UHFFFAOYSA-N 1h-1,5-naphthyridin-4-one Chemical group C1=CN=C2C(O)=CC=NC2=C1 NSPLFNGUPLZYHV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
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- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 4
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- 125000000129 anionic group Chemical group 0.000 abstract 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
本发明公开了一种稀土铕配合物及其作为发光材料的应用。所述铕配合物结构通式为Eu(ND)xAyLm,其中:ND为4-羟基-1,5-萘啶类阴离子配体,A为其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,并且x+y=3;m=0、1、2或3。这类铕配合物具有高效光致发光量子产率、优良的热稳定性和良好的载流子传输效率,可以用作光致发光和电致发光材料。
Description
技术领域
本发明涉及稀土配合物发光材料领域,特别涉及一种新型的具有高效光致发光和电致发光性能的稀土铕配合物。
背景技术
众所周知,在二十一世纪,能源将是人类社会的发展进步所必须解决的难题。在人们开发新能源的同时,“节流”也将是一重要举措。在生活耗能方面,仅照明就占耗能总量的20%左右。然而,当前照明光源对能量的利用效率仍不能达到满意的效果。LED(Light-emitting Diode)光源以其高效的能量转换率而备受关注。特别是OLED(OrganicLight-emitting Diode,有机发光二极管),它具有大面积、柔性、超薄等潜在优势,且理论发光效率高,也正在成为研究的热点。
另外,在全色彩显示方面,OLED也同样有着诱人的应用前景。目前,人们所用的彩色显示器多为阴极射线管或液晶显示。阴极射线管体积大、响应速度慢、效率低,正逐渐被淘汰。而目前市场上应用最多的液晶显示器体积小,性能也有所提高,但是也有被动式光源,视角小,响应慢等弱点。有机电致发光存在巨大的吸引力在于它具有下列特点:1、全彩色主动发光,色彩鲜艳(液晶屏需要背景光源);2、超薄显示,可柔性弯曲;3、响应速度快(液晶的100倍),视角范围宽至180°(液晶屏只有45°);4、驱动电压低,只需3-10伏的直流电压,发光效率高;5、制作简单,成本低。
所以,无论在照明还是显示方面,有机分子发光材料都有着重要的应用前景。其中,稀土发光材料由于它的独特性质而在这两方面都颇具优势。稀土配合物发光材料的优越性主要体现在:
一、窄带发射,单色性好。这对高色纯的显示器件极其有利。稀土元素有着独特的电子排布和能级结构,特别是它的4f电子层上能级丰富,稀土元素发光往往都在4f层能级之间。它能级高,同时又是内层电子,外层电子对它有屏蔽,所以它的发光受外界因素的干扰很小,才有锐利的窄带发射。对于有机小分子电致发光用于彩色显示器来说,红绿蓝(RGB)三基色需要用滤光片或其他方法来获得,从而有一定的光能浪费。稀土化合物具有色坐标小于10nm的窄带发射,因此将它应用于有机电致发光材料也具有重要意义。
二、理论上高的量子效率。纯有机荧光发光材料受到自旋统计的限制,其最大内量子效率存在理论极限(不超过25%)。相比之下,稀土配合物发光过程是由有机配体的激发单重态经系间窜越到激发三重态,再将能量传递给稀土离子使4f电子受到激发,然后回到基态而发光。由于单重态和三重态都可以传能,从理论上讲,内量子效率可达到100%。
三、配体修饰不影响发光波长。为达到好的能级匹配和载流子传导性,通常会对配体进行各种修饰,由于稀土配合物的发光基团为中心稀土离子,配体修饰不会造成光谱峰位移的变化。因此,在材料设计改性方面,稀土配合物发光材料更是具有独特的优势。
由此可见,稀土配合物具有优越的发光性能,在光致发光和电致发光领域都具有广阔应用前景。在光致发光领域,通常来说,红光铕和绿光铽的下转换光致发光材料可以用作荧光粉。目前,照明荧光灯中最常用的三基色荧光粉就是稀土绿粉(Ce,Tb)MgAl11O19、蓝粉(Ba,Mg,Eu)3Al16O27和红粉Y2O3:Eu3+。这些都是含稀土的无机固体发光材料。对于稀土有机配合物而言,其发光效率更高,只是化学稳定性和荧光热稳定性不及无机材料。所以,开发对热和紫外辐射稳定的有机配合物荧光材料可以减少稀土用量,降低成本。三价铕配合物可以高效地吸收紫外光,发射出鲜艳的红光,可以用作有机的红光下转化材料。中山大学龚孟濂等人合成了一系列含咔唑的β二酮配体的稀土Eu配合物,并将这种配合物作为下转换发光荧光粉涂覆在发近紫外光InGaN基片上,制作成发红光的LED器件(M.L.Gonget al,Appl.Phys.B,2010,99,757)。但是,在这种利用Eu配合物光致发光的LED器件中,存在着热淬灭和随电压变化可能出现混色的不稳定问题。
在电致发光领域,稀土Eu配合物在OLED方面的应用也已经有很多人做出了相关研究。目前用到的铕配体基本都是β-二酮类化合物。1991年,日本Kido等人首次利用稀土铕配合物Eu(TTA)3·2H2O作为发光材料制作有机电致发光器件,实现了窄谱带的红色发光。不久前,本课题组利用一种含噁二唑的邻菲罗啉衍生物作为中性第二配体合成了Eu(TTA)3PhO,并且制作了OLED器件,可以得到最高亮度为1086坎特拉每平方米的纯的铕红光发射,最大功率效率可达5.5流明每瓦,是Eu(TTA)3类发光材料用于OLED器件研究中的较高水平(Zhuqi Chen et al,New J.Chem.,2010,34,487)。
目前,正在研究利用的稀土铕配合物基本上都是采用β-二酮类化合物作为天线配体,其中光致发光量子产率颇高的化合物并不缺乏,但是在下转换LED材料或者是电致发光OLED中的应用却并不顺利。主要原因就是该类配体存在这一些重要缺陷:一、β-二酮结构配合物发光容易出现热淬灭。二、β-二酮结构配合物在电致发光时载流子传输性能比较差。这些缺点严重影响了β-二酮类铕配合物电致发光的效率以及它们对器件工作中温度升高的稳定性。
发明内容
本发明的目的在于提供一类新型的基于4-羟基-1,5-萘啶类配体的稀土铕配合物,用于光致发光和电致发光等方面。
本发明的铕配合物,结构通式为Eu(ND)xAyLm,其中:ND为式I所示的4-羟基-1,5-萘啶类阴离子配体,A指的是除ND以外其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,并且x+y=3;m=0、1、2或3,m的具体取值视不同的中性配体而定。
式I
式I中,R1、R2、R3、R4、R5各自独立为氢原子、卤素原子、硝基、氰基、烷基、卤素取代烷基、烯基、炔基、氨基、N-取代胺基、烷氧基、羧基、酯基、酰基、酰氨基、N-取代酰胺基、芳基或杂环芳基。
其中,所述卤素原子指F、Cl等。
上述烷基优选为C1-C24的直链或支链烷基,更优选为C1-C6的直链或支链烷基,如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基、己基等。特别优选C1-C4的直链或支链的烷基。
上述卤素取代烷基优选C1-C24的直链或支链的卤素取代烷基,优选C1-C6的直链或支链的卤素取代烷基,例如:卤代甲基、卤代乙基、卤代丙基、卤代异丙基、卤代丁基、卤代异丁基、卤代叔丁基、卤代仲丁基等,特别优选C1-C3的直链或支链的卤代烷基,例如三氟甲基、五氟乙基。
上述烯基或炔基优选C2-C24的直链或支链烯基或炔基,优选C2-C6的直链或支链烯基或炔基,特别优选C2-C4的直链或支链烯基或炔基,例如:乙烯基、乙炔基、1-丙烯基、1-丙炔基、1-丁烯基、1-丁炔基、丁二烯基等。
上述N-取代胺基优选被C1-C6烷基取代的胺基,例如二甲胺基。
上述烷氧基优选C1-C24的直链或支链烷氧基,更优选C1-C6的直链或支链烷氧基,特别优选C1-C4的直链或支链烷氧基,例如:甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基等。
上述酯基指结构为-COOR的羧酸酯基,其中R优选为C1-C24的直链或支链烷基或卤素取代烷基,更优选R为C1-C6的直链或支链烷基或卤素取代烷基,特别优选R为C1-C4的直链或支链烷基或卤素取代烷基,所述酯基例如:羧酸甲酯基、羧酸乙酯基、羧酸丙酯基、羧酸异丙酯基、羧酸丁酯基、羧酸三氟甲酯基、羧酸全氟代乙酯基等。
上述酰基指结构为-COR的基团,其中R优选为C1-C24的直链或支链烷基,更优选为C1-C6的直链或支链烷基,特别优选C1-C4的直链或支链烷基,所述酰基例如:乙酰基、丙酰基、异丙酰基、丁酰基等。
上述N-取代酰胺基优选N上的取代基为C1-C24的直链或支链烷基的酰胺基,更优选N上的取代基为C1-C6的直链或支链烷基的酰胺基,特别优选N上的取代基为C1-C4的直链或支链烷基的酰胺基,例如:N,N-二甲基甲酰胺基、N,N-二乙基甲酰胺基等。
上述芳基或杂环芳基优选C5-C10的未取代的芳基、杂环芳基或者含有取代基的芳基、杂环芳基,例如苯基、呋喃基、吡唑基、吡啶基、噁二唑基等。
当R5不是含氮或者氧配位点的基团时,本发明的4-羟基-1,5-萘啶类铕配合物结构可表示如下(式II):
式II
式II中,R1、R2、R3、R4和R5各自独立为氢原子、卤素原子、硝基、氰基、烷基、卤素取代烷基、烯基、炔基、氨基、N-取代氨基、烷氧基、羧基、酯基、酰基、酰胺基、N-取代酰氨基、芳基或杂环芳基,且R5不含氮或者氧配位点;A为除ND外的其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,并且x+y=3;m=0、1、2或3,m的具体取值视不同的中性配体而定。各类基团的优选范围如前所述。
具体的,例如如当R1、R3为甲基,R2、R4、R5为氢原子时,配合物结构式为:
当R1为氰根,R3为甲基,R2、R4、R5为氢原子时,配合物结构式为:
当R1为三氟甲基,R3为氟原子,R2、R4、R5为氢原子时,配合物结构为:
当阴离子配体A为β-二酮类配体时,配合物结构通式如下:
其中,Ra、Rb各自独立为为苯基、萘基等芳香基,或噻吩基、呋喃基、吡啶基等杂环芳基,或三氟甲基、五氟乙基等含氟烷基。优选的β-二酮阴离子配体有二苯甲酰甲烷基(DBM),三氟乙酰噻吩甲酰甲烷基(TTA),二萘甲酰甲烷基(DNM),三氟乙酰萘甲酰甲烷基(NTA)等。x=1或2,y=1或2,并且x+y=3;m=0、1、2或3。
中性配体L可以是水分子、醇分子、丙酮等配位小分子以及邻菲罗啉(phen)、联吡啶(bpy)、芳基氧磷(ArPO)类结构分子及其衍生物。
特别的,当R5为含氮或者氧配位点的基团时,所述4-羟基-1,5-萘啶类配体(ND)就成为三齿的阴离子配体,则所形成的配合物结构通式为Eu(ND)xAyLm,其中,A为除ND外的其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,且x+y=3;m=0、1或2,m的具体取值视不同的中性配体而定。该类型的三齿阴离子配体是一种新型的配体,并且具有配位稳定、配合物升华成膜性好、三个三齿阴离子配体与一个三价铕离子配位后可不再需要中性配体等优点。所以这种新型的三齿阴离子配体以及所合成的铕配合物都在该专利的保护范围内。
所述含氮配位点的基团常见的是氮杂五元环芳基和氮杂六元环芳基,例如吡咯基、咪唑基、吡啶基、噁唑基等。例如,当R5为吡啶基团时,该三齿配体与Eu形成的配合物结构通式如下(式III):
式III
如上所示,该三齿配体包括其烯醇式和酮式两种共振结构。其中,R1、R2、R3、R4如前所述;R6、R7、R8、R9独立选自氢原子、卤素原子、硝基、氰基、烷基、卤素取代烷基、氨基、N-取代胺基、烷氧基。各类基团的优选范围如前所述。A为除ND外的其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,并且x+y=3;m=0、1或2,m的具体取值视不同的中性配体而定。
所述含氧配位点的基团主要是指含羰基的基团,当R5为含羰基的基团时,该三齿配体与Eu形成的配合物结构通式如下(式IV):
式IV
如上所示,该三齿配体包括其烯醇式和酮式两种共振结构。其中,R1、R2、R3、R4如前所述;R10选自羟基、烷基、卤素取代烷基、氨基、N-取代胺基、烷氧基。各类基团的优选范围如前所述。A为除ND外的其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,并且x+y=3;m=0、1或2,m的具体取值视不同的中性配体而定。
对于式III配合物,当R1为氰根,R2、R3、R4、R6、R7、R8、R9为氢原子时,配合物结构式为:
进一步的,当x=3时,y=0,并且m=0,此时配合物的结构式为:
对于式IV配合物,当R1为氰根,R2、R3、R4为氢原子,R10为甲基时,配合物结构式为:
进一步的,当x=3时,y=0,并且m=0,此时配合物的结构式为:
本发明的4-羟基-1,5-萘啶类配体与常用的电致发光材料中的明星分子Alq3中的8-羟基喹啉结构类似,而Alq3具有非常优秀的电子传输能力。与8-羟基喹啉相比,4-羟基-1,5-萘啶类配体的HOMO能级降低,而LUMO能级几乎保持不变,所以在保证电子于LUMO能级上良好地注入和传导的同时,又能够大大增强其空穴在HOMO能级上的传导能力。基于4-羟基-1,5-萘啶类配体良好的电子和空穴传输性能,可以利用三价铕离子与该配体形成的配合物制作成红光铕的电致发光器件。
光致发光量子产率是光致发光和电致发光材料的另一个重要参数。本发明中的一种铕配合物Eu(8mCND)3L,经过升华后可以得到Eu(8mCND)3。以联吡啶钌水溶液作为参比,测得的光致发光量子产率为40%左右(乙腈溶液中,未除氧),在铕配合物中处于较高水平。
本发明中的4-羟基-1,5-萘啶类铕配合物与常用的β-二酮类铕配合物相比,具有结构刚性紧凑、热稳定性好、载流子传输能力强等优点,非常适合作为电致发光和光致发光材料。
附图说明
图1是本发明实施例5测得的Eu(8mCND)3的光致发光谱。
图2是本发明实施例5制备的电致发光器件的结构示意图。
图3是本发明实施例5的电致发光器件随电压变化的电致发光光谱图。
图4是本发明实施例5的电致发光器件的功率效率-电流效率-电压图。
具体实施方式
下面通过具体实施例对本发明的产品及其制备方法作进一步的说明,但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
本实施例中涉及到的的合成路线如下所示:
(一)8mCND(3-氰基-4-羟基-8-甲基-1,5萘啶,4-hydroxy-8-methyl-1,5-naphthyridine-3-carbonitrile)的合成:
4-甲基-3氨基吡啶3.24g(30mmol)与2-氰基-3-乙氧基丙烯酸乙酯5.07g(30mmol)混于100mL圆底烧瓶中,加入30mL甲苯,氩气保护下回流15分钟。蒸干大部分甲苯,加入石油醚立即析出产物。抽滤,二氯甲烷/石油醚(体积比1∶3)重结晶,得到中间体pre-8mCND淡黄色晶体6.51g,产率95%.1HNMR(400MHz,CDCl3,δ):10.84(br,d,J=12.8Hz,1H),8.48(s,1H),8.36(d,J=5.2Hz,1H),7.91(d,J=12.8Hz,1H),7.19(d,J=5.2Hz,1H),4.32(q,J=7.2Hz,2H),2.39(s,3H),1.38(t,J=7.2Hz,3H).MS(m/z,ESI):calcd forC12H13N3O2231,found 232(+H+).
中间体经过真空干燥后,在250mL二苯醚中投料3.25g,氩气保护下回流4h。冷却即析出产物,用少量二氯甲烷洗涤,真空干燥。粗产品需要经过升华提纯(10-1Pa,220℃),得到淡黄色产物8mCND 1.66g,产率65%。1H NMR(300MHz,D2O,Na2CO3,δ):8.11(d,J=4.5Hz,1H),7.93(s,1H),7.04(d,J=4.5Hz,1H),2.10(s,3H).MS(m/z,ESI):calcd forC10H7N3O 185,found 186(+H+).EA for C10H7N3O:C,64.86;H,3.81;N,22.69Found C,64.86;H,3.89;N,22.60.
(二)铕配合物Eu(8mCND)3phen的合成:
六水合三氯化铕366mg(1mmol)溶于20mL甲醇中,滴加邻菲罗啉(198mg,1mmol)的甲醇溶液(30mL),搅拌半小时。然后慢慢滴加8mCND的钠盐的甲醇溶液(8mCND 555mg,3mmol,NaOH 3mmol,甲醇100mL),50℃下反应2小时。浓缩反应液至30mL,析出的白色固体过滤。少量水洗,甲醇洗。真空干燥,得到铕配合物目标产物724mg,产率82%。MS(m/z,ESI):calcd for C42H26EuN11O3885,found 886(+H+).
实施例2
本实施例中涉及到的的合成路线如下所示:
(一)3m8mND(3-甲基-4羟基-8-甲基-1,5萘啶,3,8-dimethyl-1,5-naphthyridin-4-ol)的合成:
3m8mND的合成与8mCND类似,只是将原料2-氰基-3-乙氧基丙烯酸乙酯换为2-甲基-3-甲氧基丙烯酸甲酯。4-甲基-3氨基吡啶5.16g(46mmol)与2-甲基-3-甲氧基丙烯酸甲酯6.5g(50mmol)混于100mL圆底烧瓶中,加入20mL甲苯,氩气保护下回流36小时。蒸干甲苯,将析出的未反应的原料4-甲基-3氨基吡啶抽滤回收(3.5g)。滤液进行柱层析(洗脱剂:二氯甲烷/石油醚=1∶1,体积比),可以分离出中间体pre-3m8mND,同时回收原料2-甲基-3-甲氧基丙烯酸甲酯4.5g。
得到中间体pre-3m8mND白色固体488mg,产率5%.1H NMR(400MHz,CDCl3,δ):9.82(br,d,J=12.8Hz,1H),8.36(s,1H),8.12(d,J=4.8Hz,1H),7.24(d,J=12.8Hz,1H),7.07(d,J=4.8Hz,1H),3.79(s,3H),2.31(s,3H),1.88(s,3H).MS(m/z,ESI):calcd for C11H14N2O2 206,found 207(+H+).
从中间体pre-3m8mND获得3m8mND的方法同实施例1,产物3m8mND为淡黄色固体(300mg),产率77%。1H NMR(300MHz,D2O,Na2CO3,δ):8.61(d,J=4.5Hz,1H),8.00(s,1H),7.60(d,J=4.5Hz,1H),2.67(s,3H),2.24(s,3H).MS(m/z,ESI):calcd for C10H10N2O174,found 175(+H+).EA for C10H10N2O:N:16.1;C:68.95;H:5.8Found N:16.0;C:68.8;H:5.8.
(二)铕配合物Eu(3m8mND)3phen的合成:
同Eu(8mCND)3phen的合成,用3m8mND配体代替8mCND,得到铕配合物Eu(3m8mND)3phen。产率:95%。MS(m/z,ESI):calcd for C42H35EuN8O3852,found 853(+H+).
实施例3
本实施例中涉及到的的合成路线如下所示:
(一)Ac-CND(3-氰基-4羟基-6-乙酰基-1,5萘啶,6-acetyl-4-hydroxy-1,5-naphthyridine-3-carbonitrile)的合成:
Ac-CND的合成与8mCND类似,只是将原料4-甲基-3-氨基吡啶换为2-乙酰基-5-氨基吡啶。2-乙酰基-5-氨基吡啶由2-氰基-5-氨基吡啶与甲基格氏试剂反应得到。
中间体pre-AcCND产率63%.1H NMR(300MHz,CDCl3,δ):10.96(br,d,J=12.8Hz,1H),8.47(d,J=2.7Hz,1H),8.12(d,J=8.7Hz,1H),7.93(d,J=13.2Hz,1H),7.54(dd,J=8.7,2.7Hz,1H),4.34(q,J=7.2Hz,2H),2.71(s,3H),1.39(t,J=7.2Hz,3H).MS(m/z,ESI):calcd forC13H13N3O3259,found 260(+H+).
产物Ac-CND产率40%。1H NMR(300MHz,DMSO-d6,δ):13.13(br,s,1H),8.88(s,1H),8.27(d,J=8.7Hz,1H),8.19(d,J=8.7Hz,1H),2.71(s,3H).MS(m/z,ESI):calcd forC11H7N3O2 213,found 214(+H+).
3.2铕配合物Eu(Ac-CND)3的合成:
六水合三氯化铕366mg(1mmol)溶于10mL甲醇中,然后慢慢滴加Ac-CND的钠盐的甲醇溶液(Ac-CND 642mg,3mmol,NaOH 3mmol,甲醇100mL),50℃下反应2小时。蒸干溶剂。用少量水洗去盐类,用少量甲醇洗。真空干燥,得到铕配合物目标产物。产率:90%。MS(m/z,ESI):calcd for C33H18EuN9O6 789,found 790(+H+).
实施例4
本实施例中涉及到的的合成路线如下所示:
(一)pyND(6-(吡啶-2-基)-4羟基-1,5萘啶,6-(pyridin-2-yl)-1,5-naphthyridin-4-ol)的合成:
将5-氨基-2,2’-联吡啶2g(11.7mmol)、丙二酸环亚异丙酯2.52g(17.5mmol,1.5eq)、原甲酸三乙酯(8.65g,58.4mmol,5eq)混合,Ar气保护下加热至100℃。很快出现白色糊状物。5分钟后停止加热。冷却后加入50mL甲醇,滤出白色固体粉末,用甲醇洗几次。烘干,得到中间体产物pre-pyND 3.48g,产率92%。1H NMR(400MHz,CDCl3,δ):11.34(br,d,J=14.0Hz,1H),8.71~8.67(m,2H),8.63(d,J=2.7Hz,1H),8.54(d,J=8.6Hz,1H),8.40(d,J=7.9Hz,1H),7.87~7.83(m,1H),7.74(dd,J=8.9,2.7Hz,1H),7.36~7.34(m,1H),1.78(s,6H).MS(m/z,ESI):calcd for C17H15N3O4325,found 326(+H+).
从中间体到产物pyND的合成方法同8mCND。产率84%。1H NMR (400MHz,DMSO-d6,δ):11.98(br,1H),8.70~8.67(m,2H),8.60(d,J=7.9Hz,1H),8.12(d,J=9.1Hz,1H),7.94~7.88(m,2H),7.42~7.40(m,1H),6.36(d,J=7.2Hz,1H).MS(m/z,ESI):calcd forC13H9N3O 223,found 224(+H+).EA for C13H9N3O:N:18.82;C:69.95;H:4.06Found N:18.86;C:70.12;H:4.10.
(二)铕配合物Eu(pyND)3的合成:
同Eu(Ac-CND)3,用配体pyND代替Ac-CND。产率:90%。MS(m/z,ESI):calcd forC39H24EuN9O3819,found 820(+H+).EA for C39H24EuN9O3·2H2O:N:14.75;C:54.81;H:3.30Found N:14.74;C:55.45;H:3.40.
实施例5
(一)光致发光性质:
以铕配合物Eu(8mCND)3为例,以联吡啶钌水溶液作为参比,测得的光致发光量子产率为40%左右(乙腈溶液中,未除氧),在铕配合物中处于较高水平。从配合物的激发光谱(EuL3-ex)和发射光谱(EuL3-em)上来看(图1),该类型的铕配合物可以吸收紫外光,并下转换发出红光,可以用作LED中的红色荧光粉。与现在常用的无机红色荧光粉相比(比如Y2O3:Eu3+),其荧光量子产率更高。并且该配合物分子结构比较紧凑,不容易产生热淬灭,发光的热稳定性很好。将该类型的铕配合物用于LED荧光粉,可以有效地减少稀土Eu的用量,从而大大降低成本。
(二)电致发光器件的制作:
本实施例的稀土铕配合物电致发光器件所用材料包括导电玻璃(ITO)衬底层,空穴传输层选用N,N’二苯基-N,N’-二(1-萘基)-1,1’-二苯基-4,4’-二胺(NPB),发光层选用Eu(8mCND)3,空穴阻挡层为2,9-二甲基-4,7-二苯基-1,10-邻菲罗啉(BCP)、电子传输层为8-羟基喹啉铝(AlQ),阴极层为镁银合金。可以表示为ITO/NPB(30nm)/Eu∶BCPO(1∶1,20nm)/BCP(10nm)/AlQ(30nm)/Mg0.9Ag0.1(器件结构示意图见图2)。
电致发光器件可按本领域已知的方法制作,如按参考文献(Appl.Phys.Lett.1987,51,913)公开的方法制作。具体方法为:于高真空(小于8×10-5Pa)条件下,在经过清洗的导电玻璃(ITO)衬底上依次沉积空穴传输材料、发光材料、电子传输材料及阴极材料。
ITO玻璃片(有效面积3×3平方毫米),将其分别用有机溶剂超声清洗干净后,烘干,臭氧清后洗置于真空镀膜机里,在小于8×10-5Pa的高真空条件下,以石英晶体振荡器监控各层的厚度,将空穴传输材料、有机小分子、电子传输材料以及金属阴极镁银合金(Mg0.9Ag0.1)依次沉积到导电玻璃上。各有机层的厚度可以改变。
测量器件性能及电致发光光谱时,ITO电极总是与正极相连。电致发光光谱的测定是在PR650光谱仪或Hitachi F4500荧光光谱仪上,给器件施加一恒压(通常在3-30伏之间)的同时,记录其发射光谱(见图3)。
电压-电流(I-V)曲线和电压-亮度(L-V)曲线是由计算机控制的Keithley 2400Sourcemeter Unit上测定的,亮度由硅光电二极管矫正(见图4)。
该铕配合物电致发光器件在9V时起亮,15.5V时亮度达到100cd m-2,此时的功率效率为0.34lm W-1,电流效率为1.67cd A-1,最大亮度是868cd m-2。这是器件未经优化的结果,为铕配合物电致发光中的中等水平。相信经过优化处理能使其发光性能进一步提高。
Claims (10)
5.如权利要求1所述的铕配合物,其特征在于,式I中R5为含氮或者氧配位点的基团,则所述4-羟基-1,5-萘啶类配体为三齿阴离子配体,所形成的配合物Eu(ND)xAyLm中,A为除ND外的其他阴离子配体,L为中性配体;x=1、2或3,y=0、1或2,且x+y=3;m=0、1或2。
6.如权利要求5所述的铕配合物,其特征在于,所述R5为氮杂五元环芳基、氮杂六元环芳基或者是含羰基的基团。
10.权利要求1~8中任一权利要求所述的铕配合物作为发光材料的用途。
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CN104844594A (zh) * | 2015-03-24 | 2015-08-19 | 北京大学 | 离子型稀土配合物发光材料及其制备方法与应用 |
CN105017329A (zh) * | 2015-07-23 | 2015-11-04 | 北京大学 | 一类基于三齿阴离子配体的铕配合物发光材料 |
CN109796661A (zh) * | 2019-01-24 | 2019-05-24 | 淄博舜明荧光科技有限公司 | 农用荧光转光膜及其制备方法 |
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