CN114671882B - 一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂及其制备方法和应用 - Google Patents
一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种式(I)所示的三聚茚基桥联锌卟啉‑香豆素星型三重态光敏剂及其制备方法和应用,通过如下方法实现:使用2‑溴‑7,12‑双香豆素基三聚茚衍生物与硼酸酯锌卟啉衍生物通过Suzuki偶联反应制备三聚茚基桥联锌卟啉‑香豆素星型三重态光敏剂;该光敏剂在可见光区具有高的摩尔消光系数和长的三重态寿命;在589nm锌卟啉的Q带吸收下激发,用三重态能量匹配的苝二酰亚胺(PBI)或苝(Py)作为三重态湮灭剂,能够有效通过三重态‑三重态湮灭实现上转换发光;这一性能使其在太阳能电池、防伪印刷、光动力治疗、生物检测等领域有广泛应用。
Description
技术领域
本发明涉及精细有机合成和光子上转换技术领域,具体涉及一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂及其制备方法和应用。
背景技术
太阳能是人类取之不尽用之不竭的清洁能源,是解决能源危机的希望。目前人类对太阳能的利用主要集中在短波段,而太阳光在长波段(500-800nm)的光能量最强。例如近年来备受关注的太阳能电池因受到各种因素的制约,对于长波段(低能量)太阳光的利用率很低。所以人类急需研发一种技术可以吸收全光谱太阳能量,从而解决当下的能源问题。
上转换技术可以吸收长波长(低能量)处的能量,经过一系列的光物理化学过程释放出短波长(高能量)的能量,从而为解决无法充分利用太阳光能量的难题带来了希望。同时上转换技术可以广泛应用于太阳能电池、生物成像以及光催化等领域,因此上转换材料特别是光敏剂的研究受到了科学家的广泛关注。
目前,实现上转换的方法主要有双光子吸收上转换、稀土材料上转换和基于三重态-三重态湮灭(Triplet-Tripet Annihilation,TTA)机制的上转换等。与前两种上转换手段相比,TTA上转换技术所需激发光能量低;光敏剂对可见光的吸收较强;可通过选择能级相匹配的能量给体与受体实现激发波长与发射波长的调整,将不同长波段的光转换成高能量的光,从而实现大的反斯托克斯位移;同时上转换量子效率较高。
TTA上转换体系由光敏剂(能量给体)与湮灭剂(能量受体)组成。三重态光敏剂吸收激发光跃迁到激发单重态(*S1),经过系间窜越到达激发三重态(*T1),随后与能量受体发生碰撞,实现三重态-三重态能量转移,产生一个高能级的激发单重态,通过辐射跃迁产生上转换荧光回到基态。
对于三重态-三重态湮灭上转换光敏剂,要求具有高效的系间窜越能力和长寿命的三重态激发态(>10μs),以及对可见光区域的强吸收。典型方法是引入重原子(如溴、碘原子)来促进促进电子自旋耦合发生系间窜跃,有些贵金属配合物光敏剂(如钯、钌配合物)可以达到100%的系间窜跃。但此类三重态光敏剂因为制备成本高、毒性大,而且会缩短三重态寿命,限制了其在三重态光子晶体以及生物方面的应用。因而,研发新的由廉价、无毒和储藏丰富的无贵金属材料组成的三重态有机光敏剂具有重要的科学意义和应用价值。
卟啉衍生物具有较强的Soret带(420nm左右)和Q带(500~700nm)两个位于可见光区域的特征吸收,因其具有优良的电子受体能力,因此在能量转换领域一直备受关注。香豆素衍生物具有优异的光物理性质,包括很强的可见光吸收能力、荧光量子产率高、斯托克斯位移大等特点。由于香豆素的荧光光谱和锌卟啉的紫外-可见吸收光谱有大面积的重叠,有关研究表明含有香豆素及锌卟啉的二元体系存在高效的荧光共振能量转移过程,通过这一过程,可以将原本不具备系间窜越能力的香豆素作为吸收能量的给体分子,通过光致电荷将能量转移给锌卟啉受体达到增强分子体系产生三重态的能力。因此,本发明以具有大的刚性共轭结构的三聚茚为桥联单元,将两个香豆素给体分子和一个锌卟啉受体分子连接在三聚茚2,7,12位上,构成具有高效能量转移能力的星型化合物,可以作为一种新型的无贵金属三重态-三重态湮灭上转换光敏剂应用于三重态-三重态湮灭上转换技术领域。
发明内容
发明目的:针对现有技术中存在的不足,本发明的目的是提供一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂及其制备方法和在三重态-三重态湮灭上转换中的应用。
技术方案:为了实现上述发明目的,本发明采用的技术方案为:
本发明涉及的一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂及其制备方法和应用,其特征在于,其结构式如式(I)所示:
一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂的制备方法,步骤如下:
在氩气保护下,将式(II)所示的2-溴-7,12-双香豆素基三聚茚衍生物和式(III)所示的硼酸酯锌卟啉衍生物溶解于甲苯中,并于反应器中加入碳酸铯和N,N-二甲基甲酰胺,最后加入催化剂四(三苯基膦)钯,在96℃反应18~22小时;反应结束后冷却至室温,加入饱和食盐水溶液,用二氯甲烷萃取,有机层经过无水硫酸钠干燥、减压蒸除溶剂,残余物经硅胶柱层析分离提纯,洗脱剂为二氯甲烷-石油醚,得到三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)。具体化学反应式如下:
上述反应步骤中,甲苯与N,N-二甲基甲酰胺的体积比为2∶1。
上述反应步骤中,2-溴-7,12-双香豆素基三聚茚衍生物(II)与硼酸酯锌卟啉衍生物(III)的物质的量之比为1∶1。
上述反应步骤中,催化剂四(三苯基膦)钯用量为反应原料2-溴-7,12-双香豆素基三聚茚衍生物或硼酸酯锌卟啉衍生物物质的量的10%。
本发明还涉及一种上转换体系,由光敏剂和湮灭剂分散于有机溶剂中制备得到,所述光敏剂选自上述式(I)三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂,所述湮灭剂为苝二酰亚胺(PBI)或苝(Py)。
上述上转换体系中,所述光敏剂与所述湮灭剂的摩尔比为1∶6。
上述上转换体系中,所述有机溶剂为甲苯。
上述上转换体系中,所述光敏剂在所述上转换体系中的浓度为1x10-5M,所述湮灭剂浓度为6x10-5M。
本发明的有益效果
与现有技术相比,本发明的一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂及其制备和应用所具有的优点有:(1)制备方法简便易行、选择性好,避免了合成成本高、毒性大等问题;(2)该三重态湮灭上转换光敏剂具有高的摩尔消光系数(4.32×105cm-1mol- 1L)、长的三重态寿命(82.51μs)等优异的光物理性能;(3)该三重态湮灭上转换光敏剂可选择与其三重态能级相匹配的苝二酰亚胺(PBI)或苝(Py)作为湮灭剂,将其应用于三重态-三重态湮灭(TTA)上转换中,有效实现了红光向黄光或蓝光的上转换,这一性能使其在太阳能电池、防伪印刷、光动力治疗、生物检测等领域有广泛应用。
附图说明
图1为三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)的紫外-可见吸收光谱图;
图2为三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)的荧光发射光谱图;
图3为三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)在除氧甲苯溶液中的纳秒瞬态吸收光谱;
图4为三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)在除氧甲苯溶液中的衰减动力学曲线;
图5为向三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)的除氧甲苯溶液中加入苝二酰亚胺(PBI)前后的荧光发射光谱图。
图6为向三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)的除氧甲苯溶液中加入苝(Py)前后的荧光发射光谱图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明,但本发明并不限于以下实施例。
用1H-NMR、ESI-MS表征并证实三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂的结构。检测所用仪器为:Bruker ARX600型核磁共振仪(TMS为内标,氘代氯仿为溶剂),岛津UV-3100型紫外-可见分光光度计(扫描范围300~900nm,光路狭缝2nm),荧光光谱用美国Amico Bowman Series 2 Luminescence Spectrometer测试,纳秒瞬态吸收光谱用英国爱丁堡仪器LP980 laser flash photolysis spectrometer测试,使用LP900软件通过监测瞬变的衰减轨迹来记录寿命。
实施例1 三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)的制备
将2-溴-7,12-双香豆素基三聚茚衍生物(II)(0.15mmol,169mg)与meso-苯基硼酸酯锌卟啉衍生物(III)(0.15mmol,122mg)加入反应器并溶解于甲苯(20mL)中,再向反应器中加入无水碳酸铯(0.75mmol,244mg)和N,N-二甲基甲酰胺(10mL),向反应中通入氩气后,再快速加入四(三苯基膦)钯(0.015mmol,17mg),升温至96℃反应20小时,反应结束后降至室温,减压蒸除反应溶剂,残留物用二氯甲烷溶解、饱和食盐水洗涤,有机层经无水硫酸钠干燥、减压旋干溶剂,以二氯甲烷-石油醚为洗脱剂经硅胶柱层析分离提纯,得到固体产物45.6mg(产率24%)。1H-NMR(CDCl3,600MHz,ppm)δ9.10(d,J=3.6Hz,2H),8.92(d,J=4.2Hz,2H),8.82-8.86(m,4H),8.71(d,J=6.6Hz,1H),8.42(d,J=12.6Hz,3H),8.28(d,J=15.0Hz,3H),7.77(t,J=6.6Hz,5H),7.72(d,J=13.2Hz,2H),7.61(t,J=17.4Hz,4H),7.33(s,1H),7.33(s,4H),7.28(s,1H),7.25(s,1H),6.61(s,2H),6.54(s,2H),3.44(d,J=4.8Hz,8H),3.14-3.32(m,6H),2.64(s,6H),2.28-2.38(m,6H),1.24-1.28(m,18H),0.36-0.60(m,18H);UV-vis:342nm,425nm,550nm,590nm(图1);Emission Wavelength:501nm,602nm,648nm(图2);Esi-HRMS:calculated for C113H106N6O4Zn:1674.7567,found:1675.7472(M+H+)。
实施例2 三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶液紫外-可见吸收光谱
将三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶于甲苯中,配置成浓度为1×10-5M的甲苯溶液,测定其紫外-可见吸收光谱。图1为本发明实施例1制备的三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶液紫外-可见吸收光谱。
实施例3 三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶液荧光光谱
将三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶于甲苯中,配置成浓度为1×10-5M的甲苯溶液,用440nm激光激发测定其荧光发射光谱。图2为本发明实施例1制备的三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶液荧光发射光谱。
实施例4 三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)的三重态性质
将三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶于甲苯中,配置成浓度为2×10-6M的甲苯溶液。将上述溶液通入氩气鼓泡除氧15min,用427nm激光激发测定其纳秒瞬态吸收光谱。由图3可知在430nm一个基态漂白峰,与三重态-三重态湮灭上转换光敏剂(I)的稳态紫外-可见吸收光谱相对应;此外,在360-410nm和450-530nm处有两个弱的激发态吸收峰,这两个激发态吸收峰可归属为锌卟啉T1-Tn的三重态吸收峰,三重态布居在锌卟啉部分。另外在460nm激光下激发测定其衰减动力学曲线,由图4可知光敏剂(I)三重态寿命为82.51μs,证明了三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)具有良好的三重态性质。
实施例5 三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)在甲苯溶液中的上转换发光图
将三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)溶于甲苯中,配置成浓度为1×10-5M的甲苯溶液,选择苝二酰亚胺(PBI)作为湮灭剂。将上述溶液通入氩气鼓泡除氧15min,用功率为153mW的589nm激光激发。由图5可知光敏剂(I)的除氧甲苯溶液在601nm和650nm处具有红色的发射峰;当加入三重态受体苝二酰亚胺(PBI)后,在510-580nm处出现新的发射峰,并发出肉眼可见的黄光,即完成上转换发光过程。
实施例6 三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)在甲苯溶液中的上转换发光图
将三聚茚基双香豆素-锌卟啉类三重态-三重态湮灭上转换光敏剂(I)溶于甲苯中,配置成浓度为1×10-5M的甲苯溶液,选择苝(Py)作为湮灭剂。将上述溶液通入氩气鼓泡除氧15min,用功率为153mW的589nm激光激发。由图6可知光敏剂(I)的除氧甲苯溶液在601nm和650nm处具有红色的发射峰;当加入三重态受体苝(Py)后,在430-500nm处出现新的发射峰,并发出肉眼可见的蓝光,即完成上转换发光过程。
Claims (9)
1.一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I),其特征在于,该光敏剂结构式如式(I)所示:
2.权利要求1所述的一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂的制备方法,其特征在于:式(II)所示2-溴-7,12-双香豆素基三聚茚衍生物与式(III)所示硼酸酯锌卟啉衍生物通过Suzuki偶联反应得到三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I),该制备过程的反应式如下:
3.根据权利要求2所述的一种三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂的制备方法,其特征在于,由如下步骤实现:
在氩气保护下,将式(II)所示的2-溴-7,12-双香豆素基三聚茚衍生物和式(III)所示的硼酸酯锌卟啉衍生物溶解于甲苯中,并于反应器中加入碳酸铯和N,N-二甲基甲酰胺,最后加入催化剂四(三苯基膦)钯,在96℃反应18~22小时;反应结束后将体系冷却至室温,加入饱和食盐水溶液,用二氯甲烷萃取,有机层经过无水硫酸钠干燥、减压蒸除溶剂,残留物经硅胶柱层析分离提纯,洗脱剂为二氯甲烷-石油醚,得到三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂(I)。
4.根据权利要求3所述的制备方法,其特征在于所述步骤中式(II)所示的2-溴-7,12-双香豆素基三聚茚衍生物与式(III)所示的硼酸酯锌卟啉衍生物的物质的量之比为1∶1。
5.根据权利要求3所述的制备方法,其特征在于所述步骤中,催化剂四(三苯基膦)钯用量为反应原料2-溴-7,12-双香豆素基三聚茚衍生物或硼酸酯锌卟啉衍生物物质的量的10%。
6.根据权利要求3所述的制备方法,其特征在于所述步骤中,使用的溶剂为甲苯和N,N-二甲基甲酰胺,并且体积比为2∶1。
7.根据权利要求1所述的星型三重态光敏剂用于一种上转换体系,其特征在于,由光敏剂和湮灭剂分散于有机溶剂中制备得到,所述光敏剂为权利要求1所述的三聚茚基桥联锌卟啉-香豆素星型三重态光敏剂,所述湮灭剂为苝二酰亚胺(PBI)或苝(Py)。
8.根据权利要求7所述的上转换体系,其特征在于,所述有机溶剂为甲苯。
9.根据权利要求7所述的上转换体系,其特征在于,所述光敏剂在所述上转换体系中的浓度为1 x 10-5M,所述湮灭剂浓度为6 x 10-5M。
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