CN110092742B - 一种强黄色余辉发光的纯有机材料及其制备方法和应用 - Google Patents
一种强黄色余辉发光的纯有机材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种强黄色余辉发光的纯有机材料及其制备方法和应用,所述由有机化合物AX和BBr混合而成,所述AX的摩尔含量为80%~99.9%,所述BBr的摩尔含量为0.1%~20%;当BBr以0.1%~10%的浓度掺杂到ABr中时,获得的材料在紫外光激发下发射白光,磷光量子效率在12~39%之间,磷光发光寿命在90~168ms之间。当BBr以0.1%~10%的浓度掺杂到AI中时,获得的材料在紫外光激发下发射黄光,磷光量子效率在19~51%之间,磷光发光寿命在9~30ms之间。此发明涉及的材料制备方法简单,并且由于高的磷光量子效率高将使此类材料在生物成像、防伪标识等领域具有广泛的应用。
Description
技术领域
本发明涉及有机余辉发光材料技术领域,特别是涉及一种强黄色余辉发光的纯有机材料的有机材料及其制备方法和应用。
背景技术
具有室温磷光的材料已经被广泛应用于道路标识、应急标识、生物标记以及电致发光二极管等领域。其中,发光时间超过20毫秒的余辉发光材料由于其具有消除背景发射噪音的优势而备受关注。这样的材料大都是含有稀土元素的无机材料。由于分子间淬灭和振动淬灭,纯有机的余辉发光的材料鲜有报道。Adachi在雌二醇玻璃体中掺杂了不同化合物而获得发不同颜色的余辉发光材料(Adv.Funct.Mater.2013,23,3386;J.Phys.Chem.Lett.2016,7,1539)。许多含羰基的咔唑(中国专利CN104046351A、Nat.Mater.2015,14,685、Adv.Opt.Mater.2015,3,1184、Angew.Chem.Int.Ed.2016,55,2181、Adv.Mater.2017,29,1606829)、吩噻嗪、二苯并噻吩(Nat Commun.2017,8,416;Chem.Sci.,2017,8,1909)、硼酸(J.Am.Chem.Soc.2017,139,2728)和芳香酸(Phys.Chem.Chem.Phys.2015,17,15989)已经被发现具有余辉发光特性。但是这些材料的余辉发光效率大都小于10%,所以开发出具有强余辉发光的纯有机材料是十分必要的和重要的任务。
发明内容
本发明的目的是针对现有技术中存在的技术缺陷,而提供一种强黄色余辉发光的纯有机材料及其制备方法和应用,余辉发光效率大于10%,克服了纯有机余辉发光材料发光效率低下的问题。
为实现本发明的目的所采用的技术方案是:
本发明的一种强黄色余辉发光的纯有机材料,由有机化合物AX和BBr混合而成,所述AX的摩尔含量为80%~99.9%,所述BBr的摩尔含量为0.1%~20%;
AX的分子结构如下:
其中AX中X为溴或碘;
BBr的分子结构如下:
当X为溴时,AX为ABr,当X为碘时,AX为AI(下同)。
本发明的另一方面,所述强黄色余辉发光的纯有机材料晶体的制备方法,包括以下步骤:
按预定比例称取AX和BBr将其溶于良性溶剂中,完全溶解后,再在溶液表面上慢慢加入非良性溶剂,形成双层溶液,待溶剂挥发,得双组份的余辉发光的晶体材料。
在上述技术方案中,所述的良性溶剂为甲苯、苯、二氯甲烷、四氢呋喃、乙酸乙酯、三氯甲烷、氯苯、溴苯、二甲苯、丙酮、丁酮、四氯甲烷、1,2-二氯乙烷、乙酸丁酯中的一种或混合物。
在上述技术方案中,良性溶剂中AX和BBr的总摩尔浓度为0.1mM~0.1M。
在上述技术方案中,不良溶剂为石油醚、正己烷、环己烷、甲基环己烷、甲醇、乙醇、丙醇、正庚烷、正辛烷等中的一种或混合物。
在上述技术方案中,良性溶剂与不良溶剂的体积比为1:10~10:1。
本发明的另一方面,所述强黄色余辉发光的纯有机材料粉末的制备方法,包括以下步骤:
按预定比例称取AX和BBr将其溶于溶剂中,将所得溶液滴加到基质上,待溶剂挥发后得粉末状的余辉发光材料。
在上述技术方案中,所述溶剂为甲苯、苯、二氯甲烷、四氢呋喃、乙酸乙酯、三氯甲烷、氯苯、溴苯、二甲苯、丙酮、丁酮、四氯甲烷、1,2-二氯乙烷、乙酸丁酯等中的一种或混合物。
在上述技术方案中,所述溶剂中AX和BBr的总摩尔浓度为0.1mM~0.1M。
在上述技术方案中,所述基质为石英玻璃、玻璃、硅片、铁片、铝片、纸张或塑料。
本发明的另一方面,所述强黄色余辉发光的纯有机材料在生物成像、防伪标识领域中的应用。
在上述技术方案中,当所述纯有机材料由有机化合物ABr和BBr混合而成,并且BBr的摩尔含量为0.1%~10%,ABr的摩尔含量为90%~99.9%时,获得的材料在365nm紫外光激发下发射白光,关闭紫外光,所述材料发射黄色磷光,磷光量子效率为12~39%,磷光发光寿命为90~168ms。
在上述技术方案中,当所述纯有机材料由有机化合物AI和BBr混合而成,并且BBr的摩尔含量为0.1%~10%,AI的摩尔含量为90%~99.9%时,获得的材料在365nm紫外光激发下发射黄光,关闭紫外光,所述材料发射黄色磷光,磷光量子效率为19~51%,磷光发光寿命为9~30ms。
与现有技术相比,本发明的有益效果是:
本发明的双组份的余辉发光材料化合物结构简单,合成工艺容易。材料的发光颜色、磷光的发光量子效率和发光寿命可以通过调节卤素类型和双组分的摩尔比来实现。如表1和图1所示,当BBr以0.1%~10%的浓度与ABr混合时,获得的材料在紫外光激发下发射白光,磷光量子效率在12~39%之间,磷光发光寿命在90~168ms之间,表现出优秀的余辉发光性能。如表2和图2所示,当BBr以0.1%~10%的浓度与AI混合时,获得的材料在紫外光激发下发射黄光,磷光量子效率在19~51%之间,磷光发光寿命在9~30ms之间。总之,此发明涉及的材料制备方法简单,并且由于高的磷光量子效率高将使此类材料在生物成像、防伪标识等领域具有广泛的应用。
附图说明
图1是BBr掺杂在ABr中获得的材料的发射光谱。
图2是BBr掺杂在AI中获得的材料的发射光谱。
具体实施方式
以下结合附图和具体实施例对本发明作进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:
BBr的制备:苯并[b]咔唑(0.1g,0.46mmol)溶于10mLDMF中,冰水浴下搅拌10分钟。将NaH(0.06g,60%)慢慢加入上述溶液中,并在0℃下继续搅拌1个小时。将1-溴-4-(5-溴苯氧基)苯(0.17g溶于5mL DMF)溶液滴加到上述溶液中,继续搅拌2个小时,倒入200mL水中,抽滤得浅黄色固体。柱层析提纯(petroleum ether/CH2Cl2=2/1)。产率:17%.元素分析:理论值:C,71.19;H,5.55;N,2.96;实际值:C,71.15;H,5.58;N,2.93.1H NMR(400MHz,d6-DMSO)δ8.73(s,1H),8.30(d,J=7.6Hz,1H),8.08(d,J=8.3Hz,1H),8.02(d,J=8.5Hz,1H),7.97(s,1H),7.60(d,J=8.2Hz,1H),7.54(t,J=7.5Hz,1H),7.48(t,J=7.0Hz,1H),7.39(t,J=7.0Hz,1H),7.38(d,J=10.0Hz,2H),7.24(t,J=7.4Hz,1H),6.81(J=9.0Hz,2H),4.45(t,J=6.9Hz,2H),3.88(t,J=6.4Hz,2H),1.87(m,2H),1.65(m,2H),1.44(m,4H).13CNMR(101MHz,CDCl3)δ158.13,143.05,140.50,132.58,132.21,128.53,128.00,127.21,127.06,125.23,125.17,122.75,122.61,121.09,118.80,118.76,116.26,112.63,108.25,103.17,67.95,43.07,29.03,28.49,27.11,25.97.HRMS(m/z):[M+H]+calcd.forC28H27BrNO,472.1276;found,472.1279。
实施例2:
ABr的制备:根据合成BBr的条件制备ABr。得无色固体,产率:42%.元素分析:理论值:C,68.25;H,5.73;N,3.32;实际值:C,68.28;H,5.70;N,3.34.1H NMR(400MHz,CDCl3)δ8.13(d,J=7.7Hz,2H),7.53–7.46(m,2H),7.43(d,J=8.1Hz,2H),7.40–7.36(m,2H),7.28–7.21(m,2H),6.74(d,J=9.0Hz,2H),4.35(t,J=7.1Hz,2H),3.89(t,J=6.4Hz,2H),2.04–1.90(m,2H),1.80–1.67(m,2H),1.53–1.40(m,4H).13C NMR(101MHz,CDCl3)δ158.14,140.44,132.22,125.63,122.86,120.40,118.79,116.29,112.66,108.64,67.97,42.94,29.02,28.95,27.06,25.92.HRMS(m/z):[M+H]+calcd.for C24H25BrNO,422.1114;found,422.1110.
实施例3:
AI的制备:根据合成BBr的条件制备AI。得无色固体,产率:54%.元素分析:理论值:C,61.42;H,5.15;N,2.98;实际值:C,61.46;H,5.13;N,2.94.1H NMR(400MHz,CDCl3)δ8.12(s,2H),7.54(s,2H),7.51–7.46(m,2H),7.43(d,J=8.1Hz,2H),7.28–7.21(m,2H),6.64(d,J=9.0Hz,2H),4.35(t,J=7.1Hz,2H),3.88(t,J=6.4Hz,2H),1.94(m,2H),1.75(m,2H),1.49(m,4H).13C NMR(101MHz,CDCl3)δ158.89,140.42,138.17,125.62,122.85,120.39,118.78,116.90,108.63,82.50,67.82,42.93,28.99,28.94,27.05,25.91.HRMS(m/z):[M+H]+calcd.for C24H25INO,470.0981;found,470.0976.
实施例4:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取ABr 10mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入2.3微升的BBr溶液,混合均匀。在二氯甲烷溶液上面慢慢加入2mL正己烷,形成双层溶液。用封口膜封住试管,用针头扎5个针眼,室温放置一个星期,溶剂挥发完全后得无色棒状晶体。在365nm紫外光照射下,晶体发白光。当关闭紫外光,晶体能发射持续3秒的黄色磷光。磷光量子产率为22.8%,寿命为167.3毫秒。
实施例5:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取ABr 10mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入11.5微升的BBr溶液,混合均匀。在二氯甲烷溶液上面慢慢加入2mL正己烷,形成双层溶液。用封口膜封住试管,用针头扎5个针眼,室温放置一个星期,溶剂挥发完全后得无色棒状晶体。在365nm紫外光照射下,晶体发白光。当关闭紫外光,晶体能发射持续3秒的黄色磷光。磷光量子产率为35.1%,寿命为166.4毫秒。
实施例6:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取ABr 10mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入23微升的BBr溶液,混合均匀。在二氯甲烷溶液上面慢慢加入2mL正己烷,形成双层溶液。用封口膜封住试管,用针头扎5个针眼,室温放置一个星期,溶剂挥发完全后得无色棒状晶体。在365nm紫外光照射下,晶体发白光。当关闭紫外光,晶体能发射持续3秒的黄色磷光。磷光量子产率为38.5%,寿命为165.4毫秒。
实施例7:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取AI 11.1mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入2.3微升的BBr溶液,混合均匀。在二氯甲烷溶液上面慢慢加入2mL正己烷,形成双层溶液。用封口膜封住试管,用针头扎5个针眼,室温放置一个星期,溶剂挥发完全后得无色棒状晶体。在365nm紫外光照射下,晶体发黄光。当关闭紫外光,晶体能发射持续1秒的黄色磷光。磷光量子产率为31.7%,寿命为29.2毫秒。
实施例8:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取AI 11.1mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入11.5微升的BBr溶液,混合均匀。在二氯甲烷溶液上面慢慢加入2mL正己烷,形成双层溶液。用封口膜封住试管,用针头扎5个针眼,室温放置一个星期,溶剂挥发完全后得无色棒状晶体。在365nm紫外光照射下,晶体发黄光。当关闭紫外光,晶体能发射持续1秒的黄色磷光。磷光量子产率为50.7%,寿命为15.2毫秒。
实施例9:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取ABr 10mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入11.5微升的BBr溶液,混合均匀,得混合溶液。将溶液倒入一培养皿,使溶剂自然挥发,得白色粉末状固体。在365nm紫外光照射下,晶体发白光,当关闭紫外光,固体能发射持续3秒的黄色磷光。磷光量子产率为34.0%,寿命为167.2毫秒。
实施例10:
称取5.0mgBBr,溶于1mL二氯甲烷中,得0.01摩尔每升的BBr溶液。称取AI 11.1mg,加入到10mL试管中,加入2mL二氯甲烷,摇晃使固体全部溶解,加入11.5微升的BBr溶液,混合均匀得混合溶液。将溶液倒入一培养皿,使溶剂自然挥发,得白色粉末状固体。在365nm紫外光照射下,晶体发黄光,当关闭紫外光,固体能发射持续1秒的黄色磷光。磷光量子产率为48.6%,寿命为16.1毫秒。
表1.BBr掺杂在ABr中获得的材料的发光量子产率、发光寿命和CIE坐标。
表2.BBr掺杂在AI中获得的材料的发光量子产率(Φ)、发光寿命(τ)和CIE坐标。
以上所述仅是本发明的优选实施方式,应当指出的是,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
2.如权利要求1所述的强黄色余辉发光的纯有机材料的晶体制备方法,其特征在于,包括以下步骤:
按预定比例称取AX和BBr将其溶于良性溶剂中,完全溶解后,再在溶液表面上慢慢加入非良性溶剂,形成双层溶液,待溶剂挥发,得双组份的余辉发光的晶体材料;
所述的良性溶剂为甲苯、苯、二氯甲烷、四氢呋喃、乙酸乙酯、三氯甲烷、氯苯、溴苯、二甲苯、丙酮、丁酮、四氯甲烷、1,2-二氯乙烷、乙酸丁酯中的一种或混合物;
所述的不良溶剂为石油醚、正己烷、环己烷、甲基环己烷、甲醇、乙醇、丙醇、正庚烷、正辛烷等中的一种或混合物。
3.如权利要求2所述的晶体制备方法,其特征在于,所述良性溶剂中AX和BBr的总摩尔浓度为0.1mM~0.1M,良性溶剂与不良溶剂的体积比为1:10~10:1。
4.如权利要求1所述的强黄色余辉发光的纯有机材料的粉末制备方法,其特征在于,包括以下步骤:
按预定比例称取AX和BBr将其溶于溶剂中,将所得溶液滴加到基质上,待溶剂挥发后得粉末状的余辉发光材料;
所述溶剂为甲苯、苯、二氯甲烷、四氢呋喃、乙酸乙酯、三氯甲烷、氯苯、溴苯、二甲苯、丙酮、丁酮、四氯甲烷、1,2-二氯乙烷、乙酸丁酯等中的一种或混合物;
所述基质为玻璃、硅片、铁片、铝片、纸张或塑料。
5.如权利要求4所述的粉末制备方法,其特征在于,所述溶剂中AX和BBr的总摩尔浓度为0.1mM~0.1M。
6.如权利要求4所述的粉末制备方法,其特征在于,所述基质为石英玻璃。
7.如权利要求1所述的纯有机材料在余辉发光材料中的应用。
8.如权利要求7所述的应用,其特征在于,所述的纯有机材料应用于除疾病诊断或治疗外的生物成像和防伪标识领域。
9.如权利要求7所述的应用,其特征在于,当所述纯有机材料由有机化合物ABr和BBr混合而成,并且BBr的摩尔含量为0.1%~10%,ABr的摩尔含量为90%~99.9%时,获得的材料在365nm紫外光激发下发射白光,关闭紫外光,所述材料发射黄色磷光,磷光量子效率为12~39%,磷光发光寿命为90~168ms。
10.如权利要求7所述的应用,其特征在于,当所述纯有机材料由有机化合物AI和BBr混合而成,并且BBr的摩尔含量为0.1%~10%,AI的摩尔含量为90%~99.9%时,获得的材料在365nm紫外光激发下发射黄光,关闭紫外光,所述材料发射黄色磷光,磷光量子效率为19~51%,磷光发光寿命为9~30ms。
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咔唑衍生物的合成、结构及其光电性能研究;魏金贝.;《中国博士学位论文全文数据库·工程科技I辑》;20171115(第11期);B014-42 * |
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