CN106905365B - 基于三芳基磷氧化合物及其制备方法和应用 - Google Patents
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Abstract
本发明涉及具有三配位基团的磷氧化合物及其制备方法,并将它应用于有机荧光探针和光电显示领域,其结构通式为:Ph3‑nRnPO,其中R为含芳烃共轭单元的给电子基团。本发明的制备方法分离提纯操作简单,产率高。制得的化合物具有较高的分解温度和良好的热稳定性,能够很好的应用于有机荧光温度探针和光电显示领域。
Description
技术领域
本发明属于有机荧光探针领域,具体涉及一种三芳基磷氧化合物及其制备方法,并将它应用于有机荧光探针和光电显示领域。
背景技术
温度是一个最基础的物理参数,温度传感器广泛应用于日常生活和科学研究中,如:气体力学、气候与海洋研究、化学过程、医学和生物学等。传统的机械或者电子温度传感器的应用限制促使了光学温度传感器的发展,它可以实现在大面积或者流体样品甚至细胞中进行测量。在现有的光学方法,使用黑体辐射原理的红外线温度传感器的特点是灵活,易于使用,但只能测量物体表面的温度,从而限制了其应用。随着技术的发展,基于荧光的光学温度传感器因为反应速度快,空间分辨率高,以及远程处理安全已受到越来愈多的关注,具有较大的应用前景。
1997年美国麻省理工大学的Paul E.Laibinis课题组报道了激基缔合物的荧光探针,研究了温度对单体和激基缔合物发光强度的影响并得到了非常好的线性关系。受制于分子内键转动的限制,该荧光探针检测温度的范围有限。2008年法国巴黎综合理工学院的Boilot课题组报道了有机金属配合物荧光探针,该荧光探针有着很大的温度检测范围。但是,高温下的荧光量子产率较低。2011到2015年中国科学院化学研究所的杨国强课题组相继报道了一系列三芳基硼化合物,并制备了液体、微胶囊和固体温度探针检测流体和细胞中的温度分布。但是,该系列温度探针对氧气敏感,在空气中稳定性不是很好。
目前,开发一种合成简单、灵敏度高,在空气环境中稳定性好,能应用于固体和细胞中新型荧光探针是荧光温度探针的发展方向。
发明内容
针对目前荧光温度探针中存在的检测范围小、制作成本较高、稳定性差以及高温下荧光量子产率低等问题,本发明提供了一种新的有机荧光材料,即三芳基磷氧化合物,及其制备方法和应用。所述的有机荧光材料是以P=O基团为吸电子基团,连接芳烃共轭结构单元的给电子基团形成D-A结构。这类材料具有高温下荧光量子产率高,合成简单,稳定性好等优点,可在很宽的温度范围内进行原位大面积或高分辨率梯度的温度测量,可被用作比例型温度传感器。本发明采用的技术方案如下。
本发明提供了一种三芳基磷氧化合物。所述三芳基磷氧化合物,其结构通式为:
Ph3-nRnPO
其中:n=1、2或3;n表示R的个数,3-n表示苯的个数;R为含芳烃共轭单元的给电子基团,优选的,R为芳基或取代芳基,所述取代基可为C1-6烷基、C1-6烷氧基、杂环基等,例如R选自以下结构中的一种:
本发明还提供了上述三芳基磷氧化合物的制备方法,所述制备方法包括如下步骤:
(1)将RX与烷基锂反应得到RLiX,其中X为卤素;
(2)将步骤(1)中得到的产物与原料A进行反应,得到Ph3-nRnP,n=1、2或3,其中原料A为二苯基卤化磷、苯基二卤化磷、或亚磷酸三乙酯反应;
(3)步骤(2)中得到的产物与氧化剂(例如过氧化氢)进行反应,得到Ph3-nRnPO。
根据本发明,在步骤(2)中,当将步骤(1)中得到的产物与二苯基氯化磷反应,得到n=1的产物;当将步骤(1)中得到的产物与苯基二氯化磷反应,得到n=2的产物;当将步骤(1)中得到的产物与亚磷酸三乙酯反应,得到n=3的产物。
根据本发明,按摩尔比计,RX和烷基锂的比例为1:0.9~1.5;所述原料A和RX的比例为1:0.9n~1.5n;其中:n=1、2和3。所述氧化剂和原料A的比例为2:1。
根据本发明,步骤(1)中,反应在有机溶剂中进行,所述有机溶剂为乙醚。
根据本发明,所述制备方法优选包括如下步骤:
(1)在氮气保护下,RX溶于干燥的有机溶剂,温度低于-40℃条件下加入正丁基锂,搅拌2到4小时后,升温到常温后反应1到3小时。
(2)步骤(1)反应结束后,向反应体系中滴加原料A,所述原料A为亚磷酸三乙酯、二苯基卤化磷或苯基二卤化磷,氮气保护下继续反应6到24个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将步骤(2)的产物溶于有机溶剂中,滴加过氧化氢(H2O2),搅拌2-5小时。反应结束后,萃取有机相,合并有机相并浓缩,进行分离提纯,得到终产物。
上述步骤(1)中,低温反应可使用液氮冷却;所述有机溶剂为乙醚。
上述步骤(2)中,使用水和二氯甲烷萃取有机相;
上述步骤(3)中,所述有机溶剂为二氯甲烷;所述过氧化氢(H2O2)的体积浓度为30%,且过氧化氢(H2O2)和A的摩尔比例为2:1。产物通过层析柱的方法进行分离提纯。
上述制备方法中,按摩尔比计,步骤(1)中,RX和正丁基锂的比例为1:0.9~1.5,优选1:1.2;步骤(2)中,所述原料A和RX的比例为1:0.9n~1.5n,优选1:1n;其中:n=1、2和3。
所述RX和有机溶剂的添加比例为1摩尔:2~8升。优选比例为1摩尔:4~6升。
本发明还提供基于三芳基磷氧化合物在有机荧光探针和光电显示领域的用途,所述化合物可用于制备有机荧光温度探针。
通过测试本发明所述三芳基磷氧化合物在不同温度下的荧光光谱,发现所述化合物在很宽的温度范围内,随着温度变化,其荧光光谱体现出了梯度变化,且在高温下荧光量子产量高,梯度变化分辨率高。同时,该化合物具有较高的分解温度和热稳定性。这些特性使得所述化合物可用于有机荧光温度探针。该探针在不同温度下,其荧光光谱体现出不同的特点。
本发明具有如下有益效果:1、具有高温下荧光量子产率高,合成简单,稳定性好等优点。2、可在很宽的温度范围内进行原位大面积或高分辨率梯度的温度测量,可被用作比例型有机荧光温度探针。3、制得的化合物具有较高的分解温度和良好的热稳定性,能够很好的应用于有机荧光温度探针和光电显示领域。
附图说明
图1为本发明实施例1化合物的荧光吸收-发射图;
图2为本发明实施例3化合物的荧光吸收-发射图;
图3为本发明实施例5化合物的荧光吸收-发射图;
图4为本发明实施例3化合物的不同温度下的发射图;
图5为本发明实施例5化合物的不同温度下的发射图;
图6为本发明实施例5化合物的不同温度下的发射图的线性拟合曲线。
具体实施方式
为了更好理解本发明专利的内容,下面通过具体的实例来进一步说明本发明的技术方案。但这些实施实例并不限制本发明。
实施例1、
二苯基(1'-芘)氧化磷的制备
实验步骤:
(1)在氮气保护下,1-溴代芘(2g,7.6mmol,1equiv)溶于干燥的乙醚,置于干冰丙酮浴(-78℃)中冷却,低温下加入正丁基锂(5ml,7.6mmol,1equiv),搅拌2小时后,撤去干冰丙酮浴升温到常温后反应1小时。
(2)反应结束后,向反应体系中滴加二苯基氯化磷(1.71g,7.6mmol,1equiv),氮气保护下继续反应8个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将得到的固体溶于二氯甲烷中,滴加过氧化氢(H2O2)(0.17g,15.2mmol,2equiv),搅拌3小时。反应结束后,萃取有机相,合并有机相并浓缩,通过层析柱的方法进行分离提纯,得到淡黄色产物1.21g,产率43%。产物的核磁共振谱数据为:1H NMR(400MHz,CDCl3,ppm):δ8.85(d,J=9.3Hz,1H),8.21–8.07(m,3H),8.07–7.92(m,4H),7.74–7.61(m,5H),7.61–7.28(m,6H).13C NMR(400MHz,CDCl3,ppm):δ133.21,133.17,133.09,132.85,131.81,131.21,131.14,130.85,130.20,130.18,129.98,129.40,127.87,127.64,127.52,126.07,125.39,125.29,125.21,125.14,124.64,124.13,124.03,123.58,123.15,122.58,122.36.MALDI-TOFm/z:402.00[M]+.Anal.calcd for C28H19PO:C,83.57;H,4.76%;found:C,83.31;H,4.53%.
实施例2、
二苯基(1'-芘)氧化磷的制备
实验步骤:
(1)在氮气保护下,1-溴代芘(2g,7.6mmol,1equiv)溶于干燥的乙醚,置于干冰丙酮浴(-78℃)中冷却,低温下加入正丁基锂(6ml,9.1mmol,1.2equiv),搅拌2小时后,撤去干冰丙酮浴升温到常温后反应1小时。
(2)反应结束后,向反应体系中滴加二苯基氯化磷(1.14g,5.1mmol,0.67equiv),氮气保护下继续反应6个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将得到的固体溶于二氯甲烷中,滴加过氧化氢(H2O2)(0.17g,15.2mmol,2equiv),搅拌3小时。反应结束后,萃取有机相,合并有机相并浓缩,通过层析柱的方法进行分离提纯,得到淡黄色产物。
实施例3、
苯基二(1'-芘)氧化磷的制备
实验步骤:
(1)在氮气保护下,1-溴代芘(1g,3.8mmol,2equiv)溶于干燥的乙醚,置于干冰丙酮浴(-78℃)中冷却,低温下加入正丁基锂(2.5ml,3.8mmol,2equiv),搅拌2小时后,撤去干冰丙酮浴升温到常温后反应1小时。
(2)反应结束后,向反应体系中滴加苯基二氯化磷(0.34g,1.9mmol,1equiv),氮气保护下继续反应8个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将得到的固体溶于二氯甲烷中,滴加过氧化氢(H2O2)(0.043g,3.8mmol,2equiv),搅拌5小时。反应结束后,萃取有机相,合并有机相并浓缩,通过层析柱的方法进行分离提纯,得到黄色固体1.15g,产率65%。产物的核磁共振谱数据为:1H NMR(400MHz,CDCl3,ppm):δ9.10(d,J=9.3Hz,2H),8.24–8.09(m,6H),8.07–7.96(m,6H),7.92(d,J=10.1Hz,2H),7.78–7.67(m,1H),7.63(d,J=7.9Hz,2H),7.51(t,J=6.8Hz,2H)7.41(t,J=7.6Hz,2H).13C NMR(400MHz,CDCl3,ppm):δ133.45,133.37,133.23,133.20,133.28,132.26,131.65,131.55,131.44,131.34,130.90,130.80,130.14,130.04,129.50,128.80,127.94,127.71,127.59,126.93,126.54,126.08,125.68,125.62,125.45,125.35,125.13,124.31,124.28,124.18,123.26,122.76,122.62,120.69,118.82,117.27,117.14.MALDI-TOFm/z:526.10[M]+.Anal.calcd for C38H23PO:C,86.68;H,4.40%;found:C,88.51;H,4.23%.
实施例4、
苯基二(1'-芘)氧化磷的制备
实验步骤:
(1)在氮气保护下,1-溴代芘(1g,3.8mmol,2equiv)溶于干燥的乙醚,置于干冰丙酮浴(-78℃)中冷却,低温下加入正丁基锂(3.8ml,5.7mmol,3equiv),搅拌4小时后,撤去干冰丙酮浴升温到常温后反应3小时。
(2)反应结束后,向反应体系中滴加苯基二氯化磷(0.23g,1.27mmol,0.67equiv),氮气保护下继续反应24个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将得到的固体溶于二氯甲烷中,滴加过氧化氢(H2O2)(0.043g,3.8mmol,2equiv),搅拌5小时。反应结束后,萃取有机相,合并有机相并浓缩,通过层析柱的方法进行分离提纯,得到黄色固体。
实施例5、
三(1'-芘)氧化磷的制备
实验步骤:
(1)在氮气保护下,1-溴代芘(2g,7.6mmol,3equiv)溶于干燥的乙醚,置于干冰丙酮浴(-78℃)中冷却,低温下加入正丁基锂(5ml,7.6mmol,3equiv),搅拌2小时后,撤去干冰丙酮浴升温到常温后反应1.5小时。
(2)反应结束后,向反应体系中滴加亚磷酸三乙酯(0.42g,2.5mmol,1equiv),氮气保护下继续反应18个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将得到的固体溶于二氯甲烷中,滴加过氧化氢(H2O2)(0.056g,5.0mmol,2equiv),搅拌4小时。反应结束后,萃取有机相,合并有机相并浓缩,通过层析柱的方法进行分离提纯,得到淡黄色产物0.91g,产率38%。产物的核磁共振谱数据为:1H NMR(400MHz,CDCl3,ppm):δ8.74–8.63(t,J=8.6Hz,3H),8.32(dd,J=15.7,7.8Hz,2H),8.23–8.10(m,10H),8.10–7.93(m,8H),7.68–7.57(t,J=7.8Hz,2H),7.54–7.44(t,J=7.8Hz,2H).13C NMR(400MHz,CDCl3,ppm):δ151.95,139.64,134.33,134.23,133.67,133.53,132.62,132.53,131.00,130.30,130.25,130.20,130.15,130.08,139.91,129.80,129.55,128.49,127.62,127.37,127.15,127.10,126.93,126.48,126.38,126.22,126.11,125.64,125.37,125.23,125.09,124.71,124.66,124.36,124.25,124.16,123.90,123.77.MALDI-TOFm/z:650.10[M]+.Anal.calcd for C48H27PO:C,88.60;H,4.18%;found:C,88.76;H,4.13%.
实施例6、
三(1'-芘)氧化磷的制备
实验步骤:
(1)在氮气保护下,1-溴代芘(2g,7.6mmol,3equiv)溶于干燥的乙醚,置于干冰丙酮浴(-78℃)中冷却,低温下加入正丁基锂(4.5ml,6.8mmol,2.7equiv),搅拌2小时后,撤去干冰丙酮浴升温到常温后反应1.5小时。
(2)反应结束后,向反应体系中滴加亚磷酸三乙酯(0.47g,2.8mmol,1.11equiv),氮气保护下继续反应18个小时。反应结束后,萃取有机相,合并有机相并浓缩干燥,得到固体。
(3)将得到的固体溶于二氯甲烷中,滴加过氧化氢(H2O2)(0.056g,5.0mmol,2equiv),搅拌2小时。反应结束后,萃取有机相,合并有机相并浓缩,通过层析柱的方法进行分离提纯,得到淡黄色产物。
实施例7、
本实施例是对实施例1、实施例3和实施例5制备的化合物光谱的测定。将实施例1、实施例3和实施例5的化合物分别配成标准的1μM的乙腈溶液。采用日立UV-3010紫外可见光谱仪和日立F-4500荧光光谱仪进行吸收光谱和发射光谱的测定。光致发光光谱是在紫外吸收的最大吸收处测得的。具体参见图1-图3。其中,图1为实施例1化合物的荧光吸收-发射图;图2为实施例3化合物的荧光吸收-发射图;图3为实施例5化合物的荧光吸收-发射图。
实施例8、
本实施例是对实施例3制备的化合物不同温度下荧光光谱的测定。将实施例3化合物配成标准的1μM的二乙二醇二甲醚溶液。采用日立F-4500荧光光谱仪进行发射光谱的测定。光致发光光谱是在紫外吸收的最大吸收处测得的。具体结果见图4。从图中可以看出,发射光谱主要由LE态发射(360-450nm)和CT态发射(450-600nm)组成的,随着温度升高LE态强度逐渐增强,CT态强度逐渐减弱,并且二者强度之比和温度之间有一个定量的关系。
实施例9、
本实施例是对实施例5制备的化合物不同温度下荧光光谱的测定。将实施例5的化合物配成标准的1μM的二乙二醇二甲醚溶液。采用日立F-4500荧光光谱仪进行发射光谱的测定。光致发光光谱是在紫外吸收的最大吸收处测得的。具体结果见图5。从图中可以看出,实施例9中化合物光谱随温度变化的趋势与实施例8中相同,但是CT态变化更明显。
实施例10、
本实施例是对实施例5制备的化合物不同温度下荧光强度(I380nm/I480nm)的线性拟合。具体结果见图6。拟合出的公式为:I=0.942+0.073T+3.57*10-5T2+9.86*10-7T3+1.34*10-8T4-1.98*10-10T5,R2=0.99843。
Claims (1)
1.三芳基磷氧化合物在有机荧光温度探针中的用途,所述三芳基磷氧化合物为苯基二(1'-芘)氧化磷或三(1'-芘)氧化磷。
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