CN112939881B - 一种双组分有机室温磷光材料及其制备方法 - Google Patents
一种双组分有机室温磷光材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种双组分有机室温磷光材料及其制备方法,以主客体形式掺杂,合成步骤简单,成本低廉,稳定性好,干燥条件下,拥有超长的发光寿命,在254nm紫外光源激发后,黑暗条件下仍然可以持续发光,加水后,发光量子效率提高。
Description
技术领域
本发明涉及有机发光材料,特别是涉及一种有机磷光材料及其制备方法。
背景技术
有机发光材料通常包含有荧光材料、磷光材料、热活化延迟荧光材料,而有机磷光材料作为重要的组成部分之一,其重要性不言而喻。磷光材料本身是克服自旋禁阻限制,由三重激发态激子至基态的辐射跃迁,寿命达到毫秒甚至秒级。应用于光致发光、电致发光等,磷光材料能够消除荧光背景干扰,用于高级防伪及加密领域,并且还可制备高效率的磷光OLED器件。
具有超长发光寿命的有机室温磷光材料是指在关闭激发光源后仍然可以持续发光的一种有机余辉材料,区别于传统的无机余辉发光,有机长余辉发光材料由于其制备方法简单、成本低廉、易加工、生物相容性好、功能性多样,吸引了众多研究者的兴趣,并且应用于丝网印刷、数据加密防伪、生物成像等。多组分有机室温磷光材料结合功能多样性、性能优异、丰富的相互作用于一体,是构建超长发光寿命的有机余辉体系首选之一。
而蓝光和深蓝光是固态照明和全彩显示技术不可或缺的一部分,具有超长发光寿命的深蓝有机室温磷光材料,能够通过敏化实现全色域有机长余辉发光,对于探索多功能应用起到了重要的意义。但是有机蓝光长余辉因其能量高、带隙宽而不易实现。因此,开发一种具有蓝色超长磷光材料,成为当前研究的一个难点。
发明内容
发明目的:本发明的目的是提供一种双组分有机室温磷光材料,具有超长发光寿命和高量子效率的同时,还具备水响应特性;本发明的目的之二是提供一种双组分有机室温磷光材料的制备方法,制备简便、成本低廉。
技术方案:本发明所述的一种双组分有机室温磷光材料,包括主体材料和客体材料,主体材料的结构式为:
客体材料为结构式II~X中的任一种,
可选的,客体材料的结构通式为:
其中,R1、R2、R3、R4、R5为硼酸基、羧酸基、氰基、H或F原子,R6为H或N原子。
优选地,客体材料为上述物质中的式II的物质;客体材料为II时,发光效果优于其他化合物,发光寿命长达5s。
本发明还提供了一种双组分有机室温磷光材料的制备方法,包括如下步骤:制备客体材料水溶液,将主体材料分散于客体材料水溶液中,离心处理,取下层沉淀物,烘干处理,得到双组分有机室温磷光材料。
其中,主体材料的结构式为式I,客体材料取自结构式II~X中的任一种;
优选地,主体材料和客体材料的质量比为50~1500∶1;主体材料质量比过低,难以实现客体单分子发光,即406nm左右的蓝色磷光发射。
优选地,客体材料水溶液中,客体材料的浓度为1~5mg/mL。
优选地,烘干温度为30~50℃,烘干时间为24~48h。
具体包括如下步骤:将上述结构式(II)、式(III)、式(IV)、式(V)、式(VI)、式(VII)、式(VIII)、式(IX)、式(X)客体配成1mg/mL的水溶液,掺杂至三聚氰酸式(I)主体粉末中,超声5~30min,离心去除上层水溶液,在30~50℃的真空干燥箱中烘干24-48h,得到所述的具有超长发光寿命的双组分有机室温磷光材料(I-II、I-III、I-IV、I-V、I-VI、I-VII、I-VIII、I-IX、I-X)。
本发明通过双组分主客体掺杂的方法,利用强氢键网络作用,有效抑制客体在单分子状态下的非辐射跃迁,实现了具有超长发光寿命的深蓝和绿色有机室温磷光发光。
本发明的有机室温磷光材料通过双组分方式实现,分子结构通式如式(I)、式(II)、式(III)、式(IV)、式(V)、式(VI)、式(VII)、式(VIII)、式(IX)、式(X)所示。式(I)三聚氰酸是一种具有独特环状酰胺结构的有机小分子,具有多个氢键供体和受体位点,可以和少量水分子通过强的氢键作用相结合,因此三聚氰酸是用来构建复杂氢键网络的理想主体材料。
本发明中的客体材料为苯硼酸类衍生物或吡啶苯甲酸类衍生物,上式(II)、式(III)、式(IV)、式(V)、式(VI)、式(VII)、式(VIII)、式(IX)、式(X)是基于硼酸和羧酸基团衍生物,带有多个羟基,能够与主体发生强氢键作用,其本身具有磷光特性,分散于主体材料能够实现单分子的发光。由于主体材料三聚氰酸在水中的溶解性差,难以通过与客体小分子共晶产生晶体,无法利用晶体堆积的刚性环境抑制非辐射跃迁。本发明充分利用主体分子的优势,利用主体分子与客体分子基团的氢键相互作用,不用将主体材料溶解,而是将主体分子充分研磨后,客体分子水溶液与之超声和离心,将客体分子吸附在主体上。两者以主客体形式掺杂,最终得到了一种超长发光寿命的双组分有机室温磷光材料。
本发明的一种双组分有机室温磷光材料,其合成步骤简单,成本低廉,稳定性好,干燥条件下,拥有超长的发光寿命,在254nm紫外光源激发后,黑暗条件下仍然可以持续发光,加水后,发光量子效率提高。基于对水有刺激响应特性,可用于喷墨打印显示和防伪,在有机发光材料领域具有广泛的应用前景。
有益效果:
(1)本发明采用双组分有机长余辉发光体系,主体和客体通过多个氢键受体形成复杂的氢键网络,抑制了非辐射跃迁,客体分子掺杂到主体材料中,实现客体分子的单分子发光,最终得到深蓝及蓝绿色双组分有机室温磷光材料。
(2)本发明中双组分有机室温磷光材料及其制备方法,原料成本低廉,合成简单,使用溶剂绿色环保无毒害,有望实现工业化生产。
(3)本发明的一种双组分有机室温磷光材料,具有发光寿命长,量子效率高的优势。
附图说明
图1为有机室温磷光材料(I-II)的荧光和磷光发射光谱。
图2为有机室温磷光材料(I-III)的荧光和磷光发射光谱。
图3为有机室温磷光材料(I-IV)的荧光和磷光发射光谱。
图4为有机室温磷光材料(I-V、I-VI、I-VII)的磷光发射光谱。
图5为有机室温磷光材料(I-VIII、I-IX、I-X)的磷光发射光谱。
图6为有机室温磷光材料(I-II)不同含水量的磷光发射光谱。
图7为有机室温磷光材料(I-II)的动力学衰减曲线。
图8为有机室温磷光材料(I-II)与(I-X)的寿命衰减曲线。
图9为有机室温磷光材料(I-II)与原料I、II的红外光谱图。
具体实施方式
下面结合实施例对本发明进一步地详细描述。
以下实施例中的原料和试剂均可通过市售购买得到的。
实施例1:
本实施例制备有机室温磷光材料(I-II)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg对苯二硼酸(II)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL对苯二硼酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-II)。
结构如下:
如图9所示为有机室温磷光材料(I-II)与原料I、II的红外光谱图,原料I、II与有机室温磷光材料(I-II)相比,可以看出有机室温磷光材料(I-II)是共混物,没有发生化学反应。
实施例2:
本实施例制备有机室温磷光材料(I-III)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 1,3,5-苯三硼酸(III)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL1,3,5-苯三硼酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-III)。
结构如下:
实施例3:
本实施例制备有机室温磷光材料(I-IV)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 4-氰基苯硼酸(IV)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL4-氰基苯硼酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-IV)。
结构如下:
实施例4:
本实施例制备有机室温磷光材料(I-V)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 2,5-二氟苯硼酸(V)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL2,5-二氟苯硼酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-V)。
结构如下:
实施例5:
本实施例制备有机室温磷光材料(I-VI)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 3,4-二氟苯硼酸(VI)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL3,4-二氟苯硼酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-VI)。
结构如下:
实施例6:
本实施例制备有机室温磷光材料(I-VII)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 3,4,5-三氟苯硼酸(VII)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL 3,4,5-三氟苯硼酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-VII)。
结构如下:
实施例7:
本实施例制备有机室温磷光材料(I-VIII)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 2,5-吡啶二甲酸(VIII)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL2,5-吡啶二甲酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-VIII)。
结构如下:
实施例8:
本实施例制备有机室温磷光材料(I-IX)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 3,5-吡啶二甲酸(IX)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL3,5-吡啶二甲酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-IX)。
结构如下:
实施例9:
本实施例制备有机室温磷光材料(I-X)。
称量1g三聚氰酸(I)置于研钵中,研磨半个小时,称量10mg 3,4-吡啶二甲酸(X)于10mL去离子水中,搅拌过夜至溶解。取200mg研磨好的三聚氰酸于10mL离心管中,加入1mL3,4-吡啶二甲酸水溶液,剧烈震荡,超声5min,离心去除上层水溶液,置于40℃真空烘箱中24h,得到有机室温磷光材料(I-X)。
结构如下:
图1~5为上述实施例1~9得到的双组分有机室温磷光材料的荧光和磷光发射光谱,可以看出上述实施例中合成的一系列双组分材料均为磷光材料,谱带集中于400-500nm的发射,为蓝色磷光发射。
实施例10:
本实施例测试有机室温磷光材料(I-II)的水刺激响应特性。
称量100mg有机室温磷光材料(I-II)于5ml小烧杯中,加入1ml去离子水,超声5min,在60℃热台上缓慢挥发,不断监控质量,使得水质量比分别为5%及20%,得到具有不同含水量的有机室温磷光材料(I-II)。
如图6所示为不同含水量磷光强度,表明该材料具有水刺激响应特性,在水含量达到20%时,磷光强度可以提升一倍,是由于随着含水量的增加,能够显著增强主客体分子之间的氢键网络连接,从而抑制非辐射跃迁,达到磷光强度提升的效果。
如图7所示为有机室温磷光材料(I-II)的动力学衰减曲线,该材料具有超长的发光寿命,有机室温磷光材料(I-II)的磷光寿命达到5s。
将有机室温磷光材料(I-II)与有机室温磷光材料(I-X)进行寿命对比测试,如图8所示为两种主客体材料的寿命衰减曲线,表明有机磷光材料(I-II)寿命显著优异于其他材料。
对比例:
本对比例与实施例1基体相同,不同之处在于将三聚氰酸(I)改为三嗪类分子三聚氰胺I*;
结构式如下:
测试结果表明大幅降低了磷光材料的亮度和寿命。
实施例11:
本实施例以制备有机室温磷光材料(I-II)为例。
配置浓度为3.5mg/mL的客体材料水溶液,主体材料和客体材料的质量比分别设为1∶1、50∶1、1000∶1、1500∶1。
测试结果表明,当主体材料和客体材料的质量比在50~1500∶1范围内时,发光效果与实施例1效果相符。而当质量比为1∶1时,可以看出主体材料质量比过低,难以实现客体单分子发光,即406nm左右的蓝色磷光发射。
Claims (4)
3.一种权利要求1~2中任一项所述的双组分有机室温磷光材料的制备方法,其特征在于:配置客体材料水溶液,将主体材料分散于客体材料水溶液中,离心处理,取下层沉淀物,烘干处理得到双组分有机室温磷光材料,客体材料水溶液中,客体材料的浓度为1~5mg/mL。
4.根据权利要求3所述的双组分有机室温磷光材料的制备方法,其特征在于:烘干温度为30~50℃,烘干时间为24~48h。
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