CN111534298A - 基于10-苯基吩噻嗪的掺杂有机长余辉发光材料及制备和使用方法 - Google Patents
基于10-苯基吩噻嗪的掺杂有机长余辉发光材料及制备和使用方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 31
- WSEFYHOJDVVORU-UHFFFAOYSA-N 10-phenylphenothiazine Chemical compound C12=CC=CC=C2SC2=CC=CC=C2N1C1=CC=CC=C1 WSEFYHOJDVVORU-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 11
- 238000012984 biological imaging Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000007850 fluorescent dye Substances 0.000 claims description 2
- 230000005923 long-lasting effect Effects 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
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- 239000003086 colorant Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000002688 persistence Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000003335 steric effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- -1 small molecule compound Chemical class 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JLAVCPKULITDHO-UHFFFAOYSA-N tetraphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JLAVCPKULITDHO-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种基于10‑苯基吩噻嗪的掺杂有机长余辉发光材料及制备和使用方法,由客体分子X和主体分子Y构成,其结构如通式(1)所示,其中,客体发光分子X为10‑苯基吩噻嗪,主体基质分子Y可以为具有扭曲构型的芳香化合物。本发明所制备的掺杂有机长余辉发光材料具有较高的发光亮度,客体分子对主体基质材料的依赖性低,适用于各种扭曲结构的芳香化合物。此外,本发明所制备的有机长余辉材料具有不同的发光颜色和寿命,结合时间分辨技术可适用于有机光电、生物成像及多重防伪等领域。
Description
技术领域
本发明属于发光材料技术领域,涉及一种基于10-苯基吩噻嗪的掺杂有机长余辉发光材料及制备和使用方法。本发明中含有10-苯基吩噻嗪客体分子和具有扭曲结构的的芳香主体材料,通过主客体掺杂,利用主体材料充当固体溶剂作用,使客体分子均匀分散在主体材料中,通过限制客体分子的振、转动来抑制非辐射跃迁,实现长余辉发光,并利用主体材料的位阻效应进一步调节余辉寿命。本发明适用于有机光电和防伪领域。
背景技术
长余辉发光是指在撤去激发光源后仍能维持发光数秒以上(当发光的持续时间超过0.1s,亮度超过0.32mcd/m2,就能很好地通过裸眼分辨和识别,见文献:Xu S,Chen R,Zheng C,Huang W.Excited State Modulation for Organic Afterglow:Materials andApplications.Adv.Mater.2016,28(45):9920-9940.)的一种光致发光现象,又称为持续发光。长余辉发光是一种理想的信号光源,可以有效地消除常见的短寿命背景光造成的影响,从而大大提高信噪比。具有长余辉发光性能的材料也被称为夜光材料或蓄光型发光材料,这类材料在光学记录、紧急照明、交通标识、防伪、生物成像及光动力治疗等领域具有广阔的应用前景。
长余辉发光材料根据其构成可分为无机长余辉发光材料和有机长余辉发光材料两大类。其中,无机长余辉发光材料经过大量的研究已经能够实现材料发光强、稳定且持续发光时间长等良好性能,可满足商业化的要求。但是,无机长余辉发光材料不仅需要用到贵金属元素,还存在制备能耗高、工艺繁杂、透明度低等问题,难以满足广阔的市场需求和可持续发展的需要。相比之下,有机长余辉发光材料具有分子设计性强、合成容易、价格低廉、分散性佳以及生物相容性好等优点,具有更广阔的应用空间和市场前景,引起了学术界和产业界的广泛关注和研究。
由于有机长余辉材料的研发起步较晚,其种类仍然十分有限,因此,设计合成高效的有机长余辉材料仍是光电材料领域的挑战之一。目前,室温长余辉发光可以通过以下3种方法实现:(1)使用聚合物或小分子化合物为基质,掺杂磷光分子的主客体掺杂体系;(2)利用发光分子修饰聚合物,通过聚合物自身的水氧阻隔性能实现余辉的单一聚合物体系;(3)直接利用小分子自身晶体阻隔水氧的纯有机小分子晶体体系。其中,纯有机小分子晶体是目前设计有机长余辉发光材料的主流策略。但是,纯有机小分子磷光的发光效率较低,且容易被氧气猝灭,导致磷光强度低以及余辉持续时间短的问题。主客体掺杂长余辉体系可以大幅度提高余辉的持续时间,但是对主体材料的选择具有很高的依赖性,可修饰性不强,导致其种类稀少,发展缓慢,见文献:
[2]Wei J,Liang B,Duan R,Cheng Z,Li C,Zhou T,Yi Y,Wang Y.Induction ofStrong Long-Lived Room-Temperature Phosphorescence of N-Phenyl-2-naphthylamine Molecules by Confinement in a Crystalline DibromobiphenylMatrix.Angew.Chem.Int.Ed.2016,55:1-7.
[3]Kabe R,Adachi C.Organic long persistent luminescence.Nature 2017,550:384.
[4]Han J,Feng W,Muleta DY,Bridgmohan CN,Dang Y,Xie G,Zhang H,Zhou X,Li W,Wang L,Liu D,Dang Y,Wang T,Hu W.Small-Molecule-Doped Organic Crystalswith Long-Persistent Luminescence.Adv.Funct.Mater.2019,29(30):1902503.
。因此,开发一种新型的主客体掺杂有机长余辉材料,利用主体材料充当固体溶剂作用,使客体分子均匀分散在主体材料中,通过限制客体分子的振、转动来抑制非辐射跃迁,实现长余辉发光,并利用主体材料的位阻效应实现对余辉寿命(持续时间)的调控,对有机长余辉材料的发展和应用具有重要的意义。
发明内容
要解决的技术问题
为了避免现有技术的不足之处,本发明提出一种基于10-苯基吩噻嗪的掺杂有机长余辉发光材料及制备和使用方法,通过改变主体分子的结构,调节分子间相互作用,实现余辉寿命和发光颜色的调控。
技术方案
一种基于10-苯基吩噻嗪的掺杂有机长余辉发光材料,其特征在于包含客体分子和主体分子Y,其中X分散在Y中;所述客体分子X与主体分子Y的质量比为1/10~10000;通式如下:
其中,客体发光分子X为10-苯基吩噻嗪,主体分子Y为具有扭曲构型的芳香化合物。
所述具有扭曲构型的芳香化合物为如下分子中的任意一种:
其中:R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19和R20为相同或不同,采用氢原子、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基或苯基中的任意一种。
一种制备所述基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的方法,其特征在于步骤如下:
步骤1:将客体分子10-苯基吩噻嗪与主体分子按质量比1/10~10000的比例混合,加入良溶剂溶解;
步骤2:在25-65℃下加热并搅拌,使客体分子均匀分散在主体材料中获得长余辉材料。
所述的良溶剂包括但不限于二氯甲烷、三氯甲烷、乙酸乙酯、丙酮或四氢呋喃。
一种所述方法制备的基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的使用方法,其特征在于:作为发光层应用于有机电致发光器件中。
一种所述方法制备的基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的使用方法,其特征在于:作为荧光探针应用于生物成像。
一种所述方法制备的基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的使用方法,其特征在于:应用于多重防伪领域。
有益效果
本发明提出的一种基于10-苯基吩噻嗪的掺杂有机长余辉发光材料及制备和使用方法,由客体分子X和主体分子Y构成,其结构如通式(1)所示,其中,客体发光分子X为10-苯基吩噻嗪,主体基质分子Y可以为具有扭曲构型的芳香化合物。本发明所制备的掺杂有机长余辉发光材料具有较高的发光亮度,客体分子对主体基质材料的依赖性低,适用于各种扭曲结构的芳香化合物。此外,本发明所制备的有机长余辉材料具有不同的发光颜色和寿命,结合时间分辨技术可适用于有机光电、生物成像及多重防伪等领域。
本发明提供的通式所示的掺杂有机长余辉材料,选用10-苯基吩噻嗪为客体发光分子,该分子在室温下只能发射出蓝色荧光,选用具有扭曲结构的芳香化合物主体基质材料,充当固体溶剂作用,使客体分子均匀分散在主体材料中,通过限制客体分子的振、转动和阻隔水氧来抑制激发态能量的非辐射耗散,诱导其磷光发射,实现长余辉发光,进一步地,通过调控主体材料的位阻效应实现长余辉寿命的调节。
附图说明
图1是本发明提供的长余辉发光材料D1、D2、D3、D4、D5和D6的稳态光谱和延迟(50毫秒)光谱曲线。
其中,黑色曲线是稳态光谱曲线,灰色曲线是延迟光谱曲线。
图2是本发明提供的材料D1和D2晶体的荧光照片。
图3是本发明提供的材料D1、D3和D3的长余辉持续发光过程的发光照片。
图4是本发明由实施例D1、D2、D3、D4、D5和D6发光材料制备的防伪示意图。
具体实施方式
现结合实施例、附图对本发明作进一步描述:
本发明所述有机长余辉材料由客体材料X和主体材料Y构成,X均匀分散在Y中,如通式(1)所示:
通式(1)中,客体发光分子X为10-苯基吩噻嗪,主体分子Y可以为具有扭曲构型的芳香化合物,可以选自如下分子中的任意一种:
所述R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19和R20各自独自地选自氢原子、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基中的任意一种。
所述的掺杂型有机长余辉材料【通式(1)】的制备方法:
将客体分子10-苯基吩噻嗪与主体材料按质量比1/100的比例混合,加入良溶剂溶解,加热并搅拌,控制溶剂挥发速度,使客体分子均匀分散在主体材料中,待溶剂挥发完全后,获得长余辉材料。
优选地,制备方法所述的良溶剂包括二氯甲烷、三氯甲烷、乙酸乙酯、丙酮、四氢呋喃。
优选地,制备方法所述加热温度为25-65℃,例如30℃、35℃、40℃、41℃、42℃、43℃、44℃、45℃、47℃、50℃、55℃、60℃、65℃等。
以下通过具体的实施例对本发明作进一步的阐述,但本发明并不限于此特定例子。
实施例1:
长余辉发光材料D1制备:分别称取10-苯基吩噻嗪(0.01g,0.036mmol)和二苯甲酮(1g,5.49mmol)于玛瑙研钵中,加入适量的二氯甲烷溶解,在40℃的热台上缓慢研磨,待溶剂挥发完全后,得到黄色固体粉末D1。
实施例2:
参照实施例1的步骤,利用三苯基氧膦代替二苯甲酮制备得到长余辉材料D2。
实施例3:
参照实施例1的步骤,利用三苯胺代替二苯甲酮制备得到长余辉材料D3。
实施例4:
参照实施例1的步骤,利用三苯胺代替二苯甲酮制备得到长余辉材料D4。
实施例5:
参照实施例1的步骤,利用三苯基膦代替二苯甲酮制备得到长余辉材料D5。
实施例6:
参照实施例1的步骤,利用四苯基硅烷代替二苯甲酮制备得到长余辉材料D6。
表1实施例中长余辉发光材料D1-D6稳态发光波长、磷光波长和寿命
综上所述,本发明所制备的掺杂有机长余辉发光材料具有较高的发光亮度,客体分子对主体基质材料的依赖性低,适用于各种扭曲结构的芳香化合物,进一步地,还可以通过调控主体材料的位阻效应实现长余辉寿命的调节。本发明的制备方法工艺简单,重复性良好,稳定性佳,所制备的有机长余辉材料具有不同的发光颜色和寿命,结合时间分辨技术可适用于有机光电、生物成像及多重防伪等领域。以上所述,本领域的普通技术人员可以根据本发明的技术方案和技术构思作出其它各种相应的改变和变形,而所有这些改变和变形都应属于本发明权利要求的保护范围。
Claims (7)
3.一种制备权利要求1或2所述基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的方法,其特征在于步骤如下:
步骤1:将客体分子10-苯基吩噻嗪与主体分子按质量比1/10~10000的比例混合,加入良溶剂溶解;
步骤2:在25-65℃下加热并搅拌,使客体分子均匀分散在主体材料中获得长余辉材料。
4.根据权利要求3所述的方法,其特征在于:所述的良溶剂包括但不限于二氯甲烷、三氯甲烷、乙酸乙酯、丙酮或四氢呋喃。
5.一种权利要求3或4所述方法制备的权利要求1或2所述的基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的使用方法,其特征在于:作为发光层应用于有机电致发光器件中。
6.一种权利要求3或4所述方法制备的权利要求1或2所述的基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的使用方法,其特征在于:作为荧光探针应用于生物成像。
7.一种权利要求3或4所述方法制备的权利要求1或2所述的基于10-苯基吩噻嗪的掺杂有机长余辉发光材料的使用方法,其特征在于:应用于多重防伪领域。
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