CN116262728A - 一种通过柔性链调控的纯有机室温磷光材料及其制备方法与应用 - Google Patents
一种通过柔性链调控的纯有机室温磷光材料及其制备方法与应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于材料科学领域,涉及长寿命室温磷光材料,尤其涉及一种通过柔性链调控的纯有机室温磷光材料及其制备方法与应用。
背景技术
长寿命室温磷光材料(p-RTP)因其撤除激发光源后仍有余晖的性质,在生物成像、防伪加密和光存储方面也有很高的应用价值。但是,目前这些应用都是主要局限于无机化合物或金属有机化合物,例如铂(Pt)、金(Au)和铱(Ir)等配位化合物,而这一类金属配合物往往价格非常昂贵,制备过程能耗高、工艺复杂、柔性差、生物毒性大等缺点。
因此,研发纯有机室温磷光材料显得很有必要。
发明内容
本发明的目的在于克服现有技术存在的缺点与不足,提供一种通过柔性链调控的纯有机室温磷光材料及其制备方法与应用。本发明通过巧妙的分子设计,合成了一系列基于吖啶的纯有机室温磷光材料。该系列材料的磷光随着柔性链的变化,体现出光诱导室温磷光和长寿命室温磷光的特征。且该系列化合物制备简便,成本低廉,稳定性较好,可作为一种新的有机防伪材料。
本发明的目的通过下述技术方案实现:
本发明第一方面,提供一种通过柔性链调控的纯有机室温磷光材料,其结构式如式I所示,
其中,R选自C1~C6烷基中的一种。
优选地,R选自甲基、乙基、丙基、丁基、戊基、己基中的一种。
式I所示纯有机室温磷光材料,其磷光随着柔性链R的变化,体现出光诱导室温磷光和长寿命室温磷光的特征。(1)R为-CH3时,其命名为Ac-C1。Ac-C1的磷光峰在531nm,余晖颜色是绿色,寿命是543ms。(2)R为-CH2CH3时,其命名为Ac-C2。Ac-C2具有光诱导室温磷光性质,在光照前,没有肉眼可见的磷光,磷光光谱有两个峰,一个在蓝光区域435nm处寿命是8ms,在绿光区域530nm处的峰不明显,寿命是6ms。而光照30s后,蓝光区域的峰寿命达到72ms,绿光区域的峰寿命达到101ms。且蓝光区域的峰比绿光区域的峰亮度高,寿命短,所以余晖颜色也从蓝色迅速变为绿色,余晖可见3s。(3)R为-CH2CH2CH3时,其命名为Ac-C3。Ac-C3具有光诱导磷光增强的性质,磷光强度在光照30s之后增强,磷光寿命也从228ms增长到270ms。(4)R为-CH2CH2CH2CH3时,其命名为Ac-C4。Ac-C4同样具有光诱导磷光的性质,在光照前没有肉眼可见的磷光,在光照30s后,具有绿色磷光现象,且余晖现象可持续2s以上。(5)R为-CH2CH2CH2CH2CH3时,其命名为Ac-C5。Ac-C5也存在光诱导磷光,光照前没有磷光,在光照30s后,具有微弱的绿色磷光现象。(6)R为-CH2CH2CH2CH2CH2CH3时,其命名为Ac-C6。Ac-C6没有室温磷光性质,也没有光诱导室温磷光。
本发明第二方面,提供上述通过柔性链调控的纯有机室温磷光材料的制备方法,其包括如下步骤:以9,9-二烷基吖啶和对溴三氟甲苯为底物,通过C-N偶联反应制备得到。
在本发明的一个或多个实施方案中,所述的纯有机室温磷光材料的制备方法,包括如下步骤:在惰性气体氛围下,9,9-二烷基吖啶、对溴三氟甲苯、膦配体、钯催化剂和碱在溶剂中进行回流反应,得到所述的纯有机室温磷光材料。
在本发明的一个或多个实施方案中,所述的9,9-二烷基吖啶选自9,9-二甲基吖啶、9,9-二乙基吖啶、9,9-二丙基吖啶、9,9-二丁基吖啶、9,9-二戊基吖啶、9,9-二己基吖啶的一种。
在本发明的一个或多个实施方案中,所述的膦配体选自((2,4,6-三异丙基)苯基)二-环己基膦、三叔丁基膦和2-(二甲基磷酰基)乙腈中的一种或多种;优选地,所述的膦配体为三叔丁基膦。
在本发明的一个或多个实施方案中,所述的钯催化剂选自新戊酸钯、三氟乙酸钯、醋酸钯和Pd(dba)2中的一种或多种;优选地,所述的钯催化剂为醋酸钯。
在本发明的一个或多个实施方案中,所述的碱选自碳酸钠、叔丁醇钠、叔丁醇钾、氢氧化钠和氢化钠中的一种或多种;优选地,所述的碱为叔丁醇钠。
在本发明的一个或多个实施方案中,所述的溶剂选自DMF、DMSO、乙醇、甲苯、三氯甲烷、丙酮、乙酸乙酯和THF中的一种或多种;优选地,所述的溶剂为甲苯。
在本发明的一个或多个实施方案中,9,9-二烷基吖啶、对溴三氟甲苯、钯催化剂、膦配体、碱的物质的量之比为1.0:(1~5.0):(0.01~0.5):(0.01~0.5):(2.0~10.0)。
在本发明的一个或多个实施方案中,所述的回流反应时间为12~48h。
在本发明的一个或多个实施方案中,所述的纯有机室温磷光材料的制备方法还包括分离纯化步骤:向回流反应所得反应液中加入饱和食盐水,用有机萃取剂萃取,收集有机相,干燥,分离纯化、真空干燥。
本发明第三方面,提供上述通过柔性链调控的纯有机室温磷光材料在生物成像、防伪加密和光存储等方面中的应用。优选的,所述的应用为在制备防伪标志/标识中的应用。
本发明第四方面,提供一种防伪标志/标识,所述的防伪标识包括上述通过柔性链调控的纯有机室温磷光材料。优选的,所述的防伪标志/标识为防伪膜。
与现有技术相比,本发明具有以下优点和有益效果:
(1)本发明提供了一种纯有机室温磷光材料性能的有效调控策略,通过调整柔性链R基团碳链数,实现了室温磷光和光诱导室温磷光两种性质。
(2)本发明提供的纯有机光刺激响应的室温磷光材料的制备方法,其合成步骤简单、制备条件温和,适于规模化生产。
(3)本发明提供的纯有机室温磷光材料可应用于制备防伪标志、防伪标识等。
附图说明
图1为本发明纯有机室温磷光材料的余晖图;
图2为本发明纯有机室温磷光晶体的磷光曲线和寿命图;
图3为本发明纯有机光诱导室温磷光晶体的磷光寿命曲线图。
具体实施方式
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解,下面的实施例仅用于说明本发明,而不应视为限定本发明的范围。实施例中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。使用的方法如无特别说明,均为本领域公知的常规方法,使用的耗材和试剂如无特别说明,均为市场购得。除非另有说明,本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外,任何与所记载内容相似或均等的方法或材料也可应用于本发明中。
以下实施例中,通过柔性链调控的纯有机室温磷光材料(式I所示化合物)的合成路线如下所示:
实施例1:Ac-Cn的合成
合成步骤如下:
在氮气氛围下,将对溴三氟甲苯(3.6mmol)、9,9-二烷基吖啶(3mmol)、醋酸钯(0.03mmol)、三叔丁基膦(0.036mmol)和叔丁醇钠(9mmol),加入到重蒸的甲苯溶液(40mL)中,加热回流反应12小时左右。反应结束后,向反应液中加入饱和食盐水,用二氯甲烷萃取(20mL×3),收集有机相并用无水硫酸钠干燥。将产品用硅胶色谱柱层析,分离纯化,真空干燥,得最终产物,并用核磁共振氢谱,碳谱(1HNMR,13C NMR),质谱(MS),和X-射线单晶对结构进行表征,用元素分析(EA)和高效液相色谱(HPLC)对其纯度进行鉴定。
检测结果如下:
Ac-C1:白色粉末,产率为78%,熔点167℃;1H NMR(400MHz,CDCl3)δ7.79(d,J=6.4Hz,2H,ArH),7.65(s,1H,ArH),7.58(dd,J=6.4,1.6Hz,1H,ArH),7.49(dd,J=7.2,2.0Hz,2H,ArH),7.03–6.93(m,4H,ArH),6.19(dd,J=7.5,1.6Hz,2H,ArH),1.71(s,6H,-CH3).13C NMR(100MHz,CDCl3)δ140.42,131.90,130.34,128.12,128.08,128.05,126.47,125.42,121.08,113.99,36.03,31.21.MS(EI),m/z:353.00([M]+calcd for C22H18F3N:353.14);Anal.Calcd for C22H18F3N:C,74.77;H,5.13;N,3.96.Found:C,74.56;H,5.08;N,4.05.
Ac-C2:白色粉末,产率为70%,熔点148℃;1H NMR(400MHz,CDCl3)δ7.89(d,J=8.4Hz,2H,ArH),7.47–7.36(m,2H,ArH),7.35–7.29(m,2H,ArH),6.92(m,4H,ArH),6.15–6.01(m,2H,ArH),2.03(q,J=7.2Hz,4H,-CH2),0.72(t,J=7.2Hz,6H,-CH3).13C NMR(100MHz,CDCl3)δ145.23,142.11,132.19,128.23,128.20,128.16,126.60,126.38,125.27,120.66,113.70,45.32,38.28.MS(EI),m/z:380.84([M]+calcd for C24H22F3N:381.17);Anal.Calcd for C24H22F3N:C,75.57;H,5.81;N,3.67.Found:C,75.26;H,5.76;N,3.66.
Ac-C3:白色粉末,产率为73%,熔点200℃;1H NMR(400MHz,CDCl3)δ7.89(d,J=8.2Hz,2H,ArH),7.41(d,J=8.2Hz,2H,ArH),7.34(d,J=7.2Hz,2H,ArH),6.98–6.81(m,4H,ArH),6.04(d,J=9.2Hz,2H,ArH),2.03–1.83(m,4H,-CH2),1.09(dd,J=7.6Hz,4H,-CH2),0.79(t,J=7.2Hz,6H,-CH3).13C NMR(100MHz,CDCl3)δ145.24,141.61,132.19,128.20,128.16,126.53,126.31,126.20,120.62,113.69,48.73,44.25,18.33,14.59.MS(EI),m/z:409.03([M]+calcd for C26H26F3N:409.20);Anal.Calcd for C26H26F3N:C,76.26;H,6.40;N,3.42.Found:C,75.92;H,6.25;N,3.42.
Ac-C4:白色粉末,产率为65%,熔点157℃;1H NMR(400MHz,CDCl3)δ7.89(d,J=8.2Hz,2H),7.44–7.39(m,2H,ArH),7.35–7.30(m,2H,ArH),6.91(m,4H,ArH),6.11–5.99(m,2H,ArH),2.04–1.87(m,4H,-CH2),1.27–1.14(m,4H,-CH2),1.06(m,4H,-CH2),0.77(t,J=7.2Hz,6H,-CH3).13C NMR(100MHz,CDCl3)δ145.25,141.66,132.20,128.19,128.16,126.54,126.28,126.20,120.63,113.69,45.95,44.02,27.16,23.14,13.97.MS(EI),m/z:437.15([M]+calcd for C28H30F3N:437.23);Anal.Calcd for C28H30F3N:C,76.86;H,6.91;N,3.20.Found:C,76.50;H,6.78;N,3.23.
Ac-C5:白色粉末,产率为65%,熔点94℃;1H NMR(400MHz,CDCl3)δ7.88(d,J=8.0Hz,2H,ArH),7.41(d,J=8.0Hz,2H,ArH),7.34–7.28(m,2H,ArH),6.90(m,4H,ArH),6.08–6.01(m,2H,ArH),1.99–1.88(m,4H,-CH2),1.21–1.11(m,12H,-CH2),0.85–0.76(m,6H,-CH3).13C NMR(100MHz,CDCl3)δ141.65,132.19,128.18,128.14,126.51,126.25,126.20,123.33,120.62,113.67,77.22,46.07,44.09,31.67,29.79,28.84,24.91,14.05.MS(ESI),m/z:465.26([M]+calcd for C30H34F3N:466.3);Anal.Calcd for C30H34F3N:C,77.39;H,7.36;N,3.01.Found:C,77.63;H,7.34;N,3.29.
Ac-C6:白色粉末,产率为45%,熔点83℃;1H NMR(400MHz,CDCl3)δ7.88(d,J=8.0Hz,2H,ArH),7.41(d,J=8.0Hz,2H,ArH),7.31(dd,J=7.2,2.0Hz,2H,ArH),6.90(m,4H,ArH),6.05(dd,J=7.6,2.0Hz,2H,ArH),2.04–1.86(m,4H,-CH2),1.25–0.98(m,16H,-CH2),0.80(t,J=6.6Hz,6H,-CH3).13C NMR(100MHz,CDCl3)δ141.65,132.19,128.18,126.51,126.29,126.26,126.21,123.33,120.62,113.67,77.22,46.07,44.09,31.66,29.79,28.84,24.91,22.67,14.05.MS(ESI),m/z:493.30([M]+calcd for C32H38F3N:494.3);Anal.Calcd for C32H38F3N:C,77.86;H,7.76;N,2.84.Found:C,77.85;H,7.97;N,2.91.
本发明实施例中收集有机相后,是用无水Na2SO4干燥的,也可以采用其它干燥剂,只要能除去有机相中的水分且不与有机相反应即可。测试试验:
荧光光谱和磷光光谱在Hitachi F-4600荧光分光光度计上进行。用FLS980光谱仪测定所得到的6种物质的光致发光光谱、量子产率和磷光寿命。
相关结果见图1-3。Ac-C1的磷光峰在531nm,余晖颜色是绿色,寿命是543ms。Ac-C2具有光诱导室温磷光性质,在光照前,没有肉眼可见的磷光,磷光光谱有两个峰,一个在蓝光区域435nm处寿命是8ms,在绿光区域530nm处的峰不明显,寿命是6ms。而光照30s后,蓝光区域的峰寿命达到72ms,绿光区域的峰寿命达到102ms。由于435nm处的寿命比530nm处的短,余晖颜色也从蓝色迅速变为绿色,余晖可见3s。Ac-C3具有光诱导磷光增强的性质,磷光强度在光照30s之后增强,磷光寿命也从228ms增长到270ms。Ac-C4同样具有光诱导磷光的性质,在光照前没有肉眼可见的磷光,在光照30s后,具有绿光磷光现象,且余晖现象可持续2s以上。Ac-C5也存在光诱导磷光,光照前没有磷光,在光照30s后,具有绿色磷光现象。Ac-C6没有室温磷光性质,也没有光诱导室温磷光性质。
Claims (10)
2.根据权利要求1所述的通过柔性链调控的纯有机室温磷光材料,其特征在于:R选自甲基、乙基、丙基、丁基、戊基、己基中的一种。
3.权利要求1或2所述的通过柔性链调控的纯有机室温磷光材料的制备方法,其特征在于:包括如下步骤:以9,9-二烷基吖啶和对溴三氟甲苯为底物,通过C-N偶联反应制备得到。
4.根据权利要求3所述的通过柔性链调控的纯有机室温磷光材料的制备方法,其特征在于:包括如下步骤:在惰性气体氛围下,9,9-二烷基吖啶、对溴三氟甲苯、膦配体、钯催化剂和碱放入在溶剂中进行回流反应,得到所述的纯有机室温磷光材料。
5.根据权利要求4所述的通过柔性链调控的纯有机室温磷光材料的制备方法,其特征在于:所述的9,9-二烷基吖啶选自9,9-二甲基吖啶、9,9-二乙基吖啶、9,9-二丙基吖啶、9,9-二丁基吖啶、9,9-二戊基吖啶、9,9-二己基吖啶的一种。
6.根据权利要求4所述的通过柔性链调控的纯有机室温磷光材料的制备方法,其特征在于:所述的膦配体选自((2,4,6-三异丙基)苯基)二-环己基膦、三叔丁基膦和2-(二甲基磷酰基)乙腈中的一种或多种;
所述的钯催化剂选自新戊酸钯、三氟乙酸钯、醋酸钯和Pd(dba)2中的一种或多种;
所述的碱选自碳酸钠、叔丁醇钠、叔丁醇钾、氢氧化钠和氢化钠中的一种或多种;
所述的溶剂选自DMF、DMSO、乙醇、甲苯、三氯甲烷、丙酮、乙酸乙酯和THF中的一种或多种。
7.根据权利要求4所述的通过柔性链调控的纯有机室温磷光材料的制备方法,其特征在于:9,9-二烷基吖啶、对溴三氟甲苯、钯催化剂、膦配体、碱的物质的量之比为1.0:(1~5.0):(0.01~0.5):(0.01~0.5):(2.0~10.0)。
8.根据权利要求4所述的通过柔性链调控的纯有机室温磷光材料的制备方法,其特征在于:所述的回流反应时间为12~48h。
9.权利要求1或2所述的通过柔性链调控的纯有机室温磷光材料在生物成像、防伪加密、光存储中的应用。
10.一种防伪标志/标识,其特征在于:包括权利要求1或2所述的通过柔性链调控的纯有机室温磷光材料。
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