CN105601671B - 一种有机金属固体发光材料及制备方法 - Google Patents
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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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
本发明公开了一种有机金属固体发光材料及制备方法,其材料具有ABC3‑xDx或A2BC4‑xDx分子结构;式中:A为有机胺,B为金属离子,C和D为相同或不同的卤素离子,x值为0到3;其中:所述有机胺为二异丙胺、甲胺、乙胺、咪唑或咪唑衍生物;所述金属离子为锰、镉、锌或铜;其制备方法是通过有机胺和金属盐在溶液中生长出晶体得到所述发光材料。本发明材料其发光范围处于可见光范围内,发光量子产率高。其制备方法操作步骤简单,成本低,易于实施,并且安全、环保。
Description
技术领域
本发明涉及发光材料及制备方法,特别是一种有机金属发光材料及制备方法。
背景技术
发光材料广泛应用于通讯、卫星、雷达、显示、记录、光学计算机、生物分子探针等高科技领域。与无机材料相比,有机材料具有更高的发光效率和更宽的发光颜色选择范围,并且具有容易大面积成膜的优越性。从分子结构上可将有机发光材料分为(1)有机小分子(2)有机高分子(3)金属配合物。1987年C.W.Tang将8-羟基喹啉铝(Alq3)用于有机发光器件的制备(Appl Phys Lett,1987,51,913-91),极大的推动了金属有机发光材料的研究。目前,金属有机发光材料主要为金属(Ca,Be,Zn,Mg,Ga等)与羟基喹啉形成的配合物、稀土-β-二酮类配合物和稀土羧酸类配合物。例如,Burrows等研究了Gaq3和Alq3的发光性能。两者相比,Alq3的光致发光光谱强度是Gaq3的4 倍。但从驱动电压,电致发光量子效率和稳定性看,Gaq3是更好的显示器件(Appl Phys Lett,1994,64,2718-2720.)。又如,甲基 8-羟基喹啉铍(Mol.Cryst.Liq.Cyrst.Sci.Technol.Sect.A,2000,349:413)的发光颜色和Alq3相似,是绿光材料,发光波长在520nm左右。增大共轭体系,得到10-羟基苯并喹啉铍)(Chem.Lett.,1993,5:905),它的发光波长为516nm, 发光效率3151mW-1。用 (2-羟基苯基)吡啶为配体形成新的铍配合物,它的光致发光的量子效率远高于Alq3(化学学报),2001,59(1):115)。此类材料是稳定的五元环或六元环内络盐结构,有机配体通常为具有芳香性的化合物。这导致其成本较高,制备过程比较烦琐。
发明内容
本发明目的是提供一种有机金属发光材料及制备方法,该类发光材料具有光致发光,电致发光,以及上转换发光等特性,其发光范围在可见光及近红外区。具有易于制备、纯化简单,成本低廉等优点,可应用于OLED,荧光染料,信息存储等相关领域。
实现本发明目的的具体技术方案是:
一种有机金属固体发光材料,特点是该材料具有如下分子结构:
ABC3-xDx或A2BC4-xDx
式中:A为有机胺,B为金属离子,C和D为相同或不同的卤素离子,x值为0到3;其中:所述有机胺为二异丙胺、甲胺、乙胺、咪唑或咪唑衍生物;所述金属离子为锰、镉、锌或铜离子。
一种上述有机金属固体发光材料的制备方法,该方法包括以下步骤:
(1)将有机胺溶于卤化氢的水溶液、或卤化氢的甲醇、乙醇或丙酮溶液;其有机胺与卤化氢的摩尔比=1:0.01~20;有机胺溶液浓度为0.01~10.0mol/L;
(2)将金属盐溶于卤化氢的水溶液、或卤化氢的甲醇、乙醇或丙酮溶液;金属盐的浓度为0.01~1.0mol/L;金属盐与氯化氢的摩尔比=1:0.01~10;
(3)将步骤(2)的溶液加入步骤(1)溶液中,混合均匀后过滤或抽滤得到澄清溶液;
(4)将所得溶液缓慢挥发,挥发温度为5~100℃,得到分子结构为ABC3-xDx或A2BC4- xDx的晶体即所述有机金属固体发光材料;其中:
所述有机胺为二异丙胺,甲胺、乙胺、咪唑或咪唑衍生物。
所述金属盐为卤化锰、卤化锌、卤化铜或卤化镉和对应的醋酸盐。
所述发光材料其发光性能为光致发光和电致发光;其具有上转换荧光。
所述溶剂包括水、甲醇、乙醇、丙酮。
所述发光材料在OLED,荧光染料和信息存储中的应用。
本发明中合成有机金属固体发光材料反应式如下(以((CH3)2CHNHCH(CH3)2)2MnBr4为例):
(CH3)2CHNHCH(CH3)2+HBr → (CH3)2CHNH2CH(CH3)2Br
(CH3)2CHNH2CH(CH3)2Br+MnBr2 + HBr → ((CH3)2CHNHCH(CH3)2)2MnBr4
本发明以简单的有机胺类化合物为配体,与Mn,Cd,Zn,Cu等金属盐在卤化氢溶液或卤化氢的有机溶液中反应,得到一系列的具有ABC3-xDx或A2BC4-xDx分子结构的晶体。
本发明材料具有光致发光,电致发光,以及上转换发光等特性,其发光范围在可见光及近红外区。具有易于制备、纯化简单,成本低廉等优点,可应用于OLED,荧光染料,信息存储等相关领域。本发明所用试剂数量少,成本低,易于实施;整个制备过程满足绿色化学的要求,安全、环保。
附图说明
图1为本发明实施例1制备得到(CH3)2CHNHCH(CH3)2)2MnBr4晶体的发射谱,激发波长360nm;
图2为本发明实施例1制备得到(CH3)2CHNHCH(CH3)2)2MnBr4晶体的上转换发射谱,激发波长756 nm;
图3为本发明实施例1制备得到(CH3)2CHNHCH(CH3)2)2MnBr4晶体的结构图;
图4为本发明实施例3制备得到的C4H7N2MnCl3晶体的发射谱,激发波长360nm;
图5为本发明实施例3制备得到的C4H7N2MnCl3晶体的结构图;
图6为本发明实施例4制备得到的C4H7N2CdCl3晶体的磷光谱,激发波长250nm;
图7为本发明实施例4制备得到的C4H7N2CdCl3晶体的结构图。
具体实施方式
下面结合具体实施例和附图,对本发明作进一步详细说明。实施本发明的过程、条件、试剂、实验方法等,除以下专门提及的内容之外,均为本领域的普遍知识和公知常识,本发明没有特别限制内容。以下通过实施例对本发明做进一步的阐述,其目的是为了更透彻理解本发明的内容。凡所举之例不视为对本发明保护范围的限制。
实施例1
(CH3)2CHNHCH(CH3)2)2MnBr4 发光晶体的制备
本实施例以二异丙胺作为有机胺((CH3)2CHNHCH(CH3)2),溴化锰(MnBr2)作为金属盐,以HBr (47.0-49.0%)为溶剂来制备(CH3)2CHNHCH(CH3)2)2MnBr4固体有机发光材料,具体步骤如下:
(1) 室温下,将1.01g (CH3)2CHNHCH(CH3)2加入到10ml HBr (47.0-49.0%)中,配制成C6H16NBr的HBr水溶液;
(2) 室温下将2.15g MnBr2·xH2O固体溶解于20ml HBr (47.0-49.0%)中,配制成MnBr2的HBr水溶液;
(3) 将步骤(2)制得的溶液加入到步骤(1)制得的溶液中,混合均匀;
(4) 在30℃下缓慢挥发,24小时左右晶体逐渐长出。
对本实施例制备得到的(CH3)2CHNHCH(CH3)2)2MnBr4晶体进行固体荧光光谱测试,结果如图1所示,证明了其发光为绿光,并具有良好的发光性能。图2证实了其双光子吸收性能。图3为其晶体结构。
实施例2
C4H7N2MnCl3固体有机发光材料的制备
本实施例以1-甲基咪唑(C4H6N2)、MnCl2·4H2O和HCl ( 40%)为原料,来制备C4H7N2MnCl3固体有机发光材料,具体步骤如下:
(1) 室温下,将10ml HCl (40%)溶液逐滴加入到1g C4H6N2中,静置;
(2) 将2g MnCl2·4H2O溶解于20 ml HCl ( 40%)中溶液,配制成MnCl2 的HCl 水溶液;
(3) 将步骤(2)制得的溶液加入到步骤(1)制得的溶液中;
(4) 将混合液缓慢挥发,24小时左右晶体逐渐长出。
对本实施例制备得到的C4H7N2MnCl3晶体进行固体荧光光谱测试,结果如图4所示,证明了其发光为黄光,并具有良好的发光性能。图5为其晶体结构。
实施例3
C4H7N2CdCl3固体有机发光材料的制备
本实施例以1-甲基咪唑(C4H6N2)、Cd(CH3COO)2和HCl (40%)为原料,来制备C4H7N2CdCl3固体有机发光材料,具体步骤如下:
(1) 将0.01 mol 1-甲基咪唑加入到0.01mol盐酸(HCl)中;
(2) 向0.01 mol Cd(CH3COO)2中加入10ml去离子水,超声2分钟溶解;
(3) 将步骤(2)制得的溶液滴加到步骤(1)制得溶液中,有白色絮状物产生,抽滤得到白色固体
(4) 用去离子水将白色固体进行超声2分钟溶解,放在室温下重结晶,挥发生长,2周后得到针状无色晶体。
对本实施例制备得到的C4H7N2CdCl3金属有机晶体进行磷光检测和单晶检测,其结果如图6和图7所示。
Claims (5)
1.一种有机金属固体发光材料,其特征在于该材料具有如下分子结构:
A2BC4-xDx
式中:A为有机胺,B为金属离子,C和D为相同或不同的卤素离子,x值为0;其中:A2BC4-xDx分子结构中的有机胺为质子化二异丙胺,金属离子为锰,卤素离子为溴。
2.一种权利要求1所述有机金属固体发光材料的制备方法,其特征在于该方法包括以下步骤:
(1)将有机胺溶于卤化氢的水溶液、或卤化氢的甲醇、乙醇或丙酮溶液;其有机胺与卤化氢的摩尔比=1:0.01~20;
(2)将金属盐溶于卤化氢的水溶液、或卤化氢的甲醇、乙醇或丙酮溶液;金属盐与氯化氢的摩尔比=1:0.01~10;
(3)将步骤(2)的溶液加入步骤(1)溶液中,混合均匀;
(4)将所得溶液缓慢挥发,挥发温度为5~100℃,得到分子结构为A2BC4-xDx的晶体即所述有机金属固体发光材料;其中:
所述有机胺为质子化二异丙胺;所述金属盐为卤化锰和对应的醋酸盐。
3.根据权利要求1所述的金属固体发光材料,其特征在于其发光性能为光致发光和电致发光。
4.根据权利要求1所述的金属固体发光材料,其特征在于其具有上转换荧光。
5.一种权利要求1所述的金属固体发光材料的应用,其特征在所述材料在OLED,荧光染料和信息存储中的应用。
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