CN114195801B - 基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料 - Google Patents
基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料 Download PDFInfo
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Abstract
本发明属于有机光电材料领域，具体涉及一种基于3‑烷氧基‑4‑氰基噻吩的近红外有机光电分子材料及其制备方法和应用。本发明将3‑烷氧基‑4‑氰基噻吩结构用于构筑近红外有机光电受体分子，其中烷氧基与中心单元部分形成强给电子共轭效应，氰基与末端单元形成强拉电子共轭效应，能够同时提升前者的给电子能力与后者的受电子能力。烷氧基与氰基用于修饰分子骨架结构，可以有效提升分子的介电常数，有利于光电过程中激子的解离，提高自由电荷的产生效率。且易溶于常见有机溶剂，以利于溶液旋涂法制备高质量薄膜。所制备的有机光电分子薄膜吸收光谱范围超过1.2μm，应用于有机光电探测器件，表现出优异的性能。
Description
技术领域
本发明属于有机光电材料领域，具体涉及一种基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料及其制备方法和应用。
背景技术
有机光电材料结构丰富、制备廉价、可溶液加工、适应大面积与柔性器件，在发光器件、场效应晶体管、光伏电池等领域都具有良好的应用潜力。吸收光谱达到近红外区，特别是大于1微米的有机光电材料，可用于有机光探测器件，实现对近红外光信息的检测，在图像传感、生物医学检测、光通信、环境监测、夜视、远程控制等方面具有广阔的应用前景(Science2009,325,1665-1667)。经过二十多年的发展，有机光探测器的性能已经可以与商业硅探测器媲美(Appl.Phys.Lett.2020，117,093302)。
目前,基于富勒烯受体的传统有机光探测材料体系面临着性能与稳定性双重限制，逐渐被非富勒烯有机光探测材料体系所替代。高性能的近红外有机光电探测材料，如IEICO-4F、CO1-4Cl、COi8DFIC、Y6、FOIC、F8IC、IFIC-i-4F、PDTTIC-4F(Semicond.Sci.Technol.2020,35,114001；Acs Appl.Mater.Inter.2020,12,17781-17787；J.Am.Chem.Soc.2021,143,11,4281–4289)等均为A-D-A型结构的分子。该类分子(A-D-A型)在光电信号转换过程中其具有多重优势：1.近红外波段吸光系数高达105cm-1量级；2.末端平面受体可以实现分子间的pi轨道耦合，利于电荷分离与跳跃传输；3.HOMO、LUMO轨道在整个分子高度离域，利于电荷传输；4.能级和带隙容易调控；5.光化学稳定性好；6.活性层形貌稳定性好。然而，该类分子的光吸收目前尚未覆盖大于1.2μm范围，严重限制了相应有机光探测器的应用场景和范围。
上述高性能近红外有机光电探测分子是通过增强给体单元的电子密度来降低分子带隙，实现宽光谱吸收，效果有限。
发明内容
针对上述存在问题或不足，为解决现有有机光电材料种类匮乏、以及吸收光谱相对较小的问题，本发明提供了一种基于3-烷氧基-4-氰基噻吩的近红外有机光电探测分子材料及其制备方法和应用。
一种基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料，其结构通式如式I所示：
其中，R为C1-C25的烷基或氧、氮、硫、硅、氟、氯原子取代的烷基，且R为相同或不同。
所述D单元选自式II中任意一种：
其中，R1-R9为C1-C25的烷基或氧、氮、硫、硅、氟、氯原子取代的烷基，且R1-R9为相同或不同。
所述A单元选自式III中任意一种：
其中，X、Y为氢、氟、氯、溴、甲基中的一种，且X和Y不同。
上述基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料的制备方法，包括以下步骤：
步骤1、合成式IV所示化合物：将式V所示化合物先与正丁基锂完全溶于有机溶剂，于-90～-20℃，在惰性氛围下反应0.5-3小时；然后再加入N,N-二甲基甲酰胺于-90～-20℃，在惰性氛围下反应3-18小时，即得。
其中，式V所示化合物、正丁基锂和N,N-二甲基甲酰胺的摩尔比为1:1～1.5:2-20；所述有机溶剂为四氢呋喃、正己烷或乙醚。
式中，R采用C1-C25的烷基或氧、氮、硫、硅、氟、氯原子取代的烷基。
步骤2、合成式VI所示化合物：将步骤1所得式IV化合物和N-溴代琥珀酰亚胺按摩尔比1:1～20完全溶于有机溶剂，于25～120℃反应1～48小时，即得。
所述有机溶剂为四氢呋喃、三氯甲烷或1,2-二氯乙烷。
步骤3、合成式VII所示化合物：将式VIII和步骤2所得式VI化合物按摩尔比为1:2～6完全溶于有机溶剂，并加入催化剂于100～120℃，在惰性氛围下反应12～72小时，即得。
所述有机溶剂为甲苯、氯苯或邻二氯苯，催化剂为Pd(PPh3)4、Pd(OAc)2或Pd(PPh3)2Cl2。
式VIII中，D采用式II中任意一种。
步骤4、合成式I所示化合物：将步骤3所得式VII化合物和式IX所示化合物按摩尔比为1:2～1:10完全溶于反应溶剂，并加入反应催化剂于30～80℃回流反应12～48小时，即得。
所述催化剂为三乙胺、吡啶或哌啶；反应溶剂为三氯甲烷、四氢呋喃或1，2-二氯乙烷。
进一步的，所述步骤1中式V化合物、正丁基锂和N,N二甲基甲酰胺的摩尔比为1:1.1:8，反应有机溶剂为四氢呋喃，反应温度均为-78℃，在先反应为1小时，在后反应为12小时。
进一步的，所述步骤2中式IV化合物和N-溴代琥珀酰亚胺的投料摩尔比为1:4，有机溶剂为四氢呋喃，反应温度为80℃，反应时间为12小时。
进一步的，所述步骤3中催化剂为四(三苯基膦)钯Pd(PPh3)4，式VIII和式VI化合物的投料摩尔比为1：4，反应温度为110℃，反应时间为48小时，有机溶剂为甲苯。
进一步的，所述步骤4中式VII化合物和式IX化合物的投料摩尔比为1:10，反应温度为60℃，反应时间为12小时；反应催化剂为吡啶，反应溶剂为三氯甲烷。
进一步的，以本发明提供的基于3-烷氧基-4-氰基的近红外有机光电分子材料为受体材料，PTB7-Th或P3HT为给体材料，作为光敏活性层，通过溶液旋涂制备有机光电探测器件(如二极管型)。
本发明通过3-烷氧基-4-氰基噻吩核心单元的引入，可以在增强给体单元的电子密度基础上，同时实现受体单元的电子密度降低，有效增强给受体单元间的电荷转移效应，显著降低分子带隙，实现更宽的光谱吸收和探测能力。
本发明的有益效果是：
1、本发明将3-烷氧基-4-氰基噻吩结构应用于构筑近红外有机光电受体分子，其中烷氧基与中心单元部分形成强给电子共轭效应，氰基与末端单元形成强拉电子共轭效应，能够同时提升前者的给电子能力与后者的受电子能力，显著增强分子内电荷转移效应，降低分子带隙，所制备的有机光电分子薄膜吸收光谱范围超过1.2μm。
2、本发明将烷氧基与氰基用于修饰分子骨架结构，可以有效提升分子的介电常数，有利于光电过程中激子的解离，提高自由电荷的产生效率。
3、本发明的基于3-烷氧基-4-氰基的近红外有机光电分子在常见的有机溶剂(如三氯甲烷、四氢呋喃、甲苯)中有良好的溶解性，可以用溶液旋涂的方法制备高质量的薄膜。
附图说明
图1为实施例1中有机光电分子CN5T的合成路线图；
图2为实施例2中有机光电分子CN4T的合成路线图；
图3为实施例1中有机光电分子CN5T的薄膜吸收光谱图。
具体实施方式
下面结合附图和实施例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1、CN5T的合成
化学反应流程图如图1所示，具体反应步骤和反应条件如下：
化合物2(图1中标号为2的化合物)的制备：在惰性氛围下，化合物1(图1中标号为1的化合物)(2.37g,10mmol)的无水四氢呋喃(100mL)溶液降至-78℃，缓慢滴加入正丁基锂(2.4M,4.17mL)溶液，搅拌反应1h。然后在温度-78℃下将干燥的N，N-二甲基甲酰胺(1.46g,20mmol)缓慢加入，搅拌反应1h。反应液升至室温继续反应3h，然后加水5mL淬灭反应。反应液用二氯甲烷萃取，水洗三次，无水硫酸镁干燥。有机相旋转蒸发除去溶剂，以石油醚：二氯甲烷(1:1)为洗脱剂，用硅胶层析柱分离，旋转蒸发除去溶剂后得到淡黄色油状产物2(2.02g,76％)EI MS:m/z 265.4。
化合物3(图1中标号为3的化合物)的制备：在惰性氛围下，化合物2(2.02g,7.6mmol)的四氢呋喃(50mL)溶液中加入NBS(2.70g,15.2mmol)，升温至80℃搅拌反应6h。加水100mL淬灭反应，应液用二氯甲烷萃取，水洗三次，无水硫酸镁干燥。有机相旋转蒸发除去溶剂，以石油醚：二氯甲烷(1:1)为洗脱剂，用硅胶层析柱分离，旋转蒸发除去溶剂后得到浅色油状产物3(1.47g,56％)EI MS:m/z 344.3。
化合物5(图1中标号为5的化合物)的制备：在惰性氛围下，化合物3(1.47g,4.26mmol)和化合物4(图1中标号为4的化合物)(1.85g，1.42mmol)的无水甲苯(30mL)溶液中，加入Pd(PPh3)4(116mg,0.1mmol)。整个反应体系加热到110℃搅拌48个小时。反应液冷却后，加入甲醇沉析，离心，固体部分用氯仿溶解，水洗三次，无水硫酸镁干燥。有机相旋转蒸发除去溶剂，以石油醚：二氯甲烷(3:1)为淋洗剂，用硅胶层析柱分离，旋转蒸发除去溶剂后得到紫色固体产物5(1.32g,74％)，MS(MALDI-TOF):m/z＝1256.0。
化合物CN5T的制备：惰性氛围下，化合物5(126mg,0.1mmol)、化合物6(图1中标号为6的化合物)(115mg,0.5mmol)、吡啶(0.2mL)的无水氯仿(15ml)溶液，加热到60℃搅拌12个小时。等反应液冷却下来，加入甲醇沉析，离心，固体部分用氯仿溶解，水洗三次，无水硫酸镁干燥。有机相旋转蒸发除去溶剂，以石油醚：三氯甲烷(2：1)做淋洗剂，用硅胶层析柱分离产物。产物再用氯仿和甲醇、二氯甲烷重结晶，得到蓝黑色固体产物CN5T(108mg，64％)，MS(MALDI-TOF):m/z＝1680.3。
实施例2、CN4T的合成
化学反应流程图如图2示，具体反应步骤和反应条件如下：
化合物8(图2中标号为8的化合物)的制备：在惰性氛围下，化合物3(1.47g,4.26mmol)和化合物7(图2中标号为7的化合物)(1.39g，1.42mmol)的无水甲苯(30mL)溶液中，加入Pd(PPh3)4(116mg,0.1mmol)。整个反应体系加热到110℃搅拌48个小时。反应液冷却后，加入甲醇沉析，离心，固体部分用氯仿溶解，水洗三次，无水硫酸镁干燥。有机相旋转蒸发除去溶剂，以石油醚：二氯甲烷(4:1)为淋洗剂，用硅胶层析柱分离，旋转蒸发除去溶剂后得到紫色固体产物-化合物8(0.91g,69％)，MS(MALDI-TOF):m/z＝929.4。
化合物CN4T的制备：惰性氛围下，化合物8(92.9mg,0.1mmol)、化合物6(115mg,0.5mmol)、吡啶(0.2mL)的无水氯仿(15ml)溶液，加热到60℃搅拌12个小时。等反应液冷却下来，加入甲醇沉析，离心，固体部分用氯仿溶解，水洗三次，无水硫酸镁干燥。有机相旋转蒸发除去溶剂，以石油醚：二氯甲烷(2：1)做淋洗剂，用硅胶层析柱分离产物。产物再用氯仿和甲醇、二氯甲烷重结晶，得到蓝黑色固体产物CN4T(92mg，68％)，MS(MALDI-TOF):m/z＝1353.7。
实施例3测定有机光电分子CN5T在薄膜状态下的紫外-可见-近红外吸收光谱：将有机光电分子CN5T溶解于氯仿中配成20mg/mL浓度的溶液并取部分溶液旋涂至石英片上制成薄膜。在薄膜状态下测得的吸收光谱如图3所示，吸收光谱超过了1.2μm。
通过以上实施例可见，本发明将3-烷氧基-4-氰基噻吩结构应用于构筑近红外有机光电受体分子，其中烷氧基与中心单元部分形成强给电子共轭效应，氰基与末端单元形成强拉电子共轭效应，能够同时提升前者的给电子能力与后者的受电子能力，显著增强分子内电荷转移效应，降低分子带隙，所制备的有机光电分子薄膜吸收光谱范围超过1.2μm。烷氧基与氰基用于修饰分子骨架结构，可以有效提升分子的介电常数，有利于光电过程中激子的解离，提高自由电荷的产生效率。且易溶于常见有机溶剂，以利于溶液旋涂法制备高质量薄膜。将本发明的3-烷氧基-4-氰基的近红外有机光电分子材料为受体材料，PTB7-Th或P3HT为给体材料，作为光敏活性层制备有机光电探测器件，表现出优异的性能。
Claims (3)
1.一种基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料，其特征在于：
为化合物CN5T，结构式如下所示：
2.如权利要求1所述基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料的应用方法，其特征在于：以基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料为受体材料，PTB7-Th或P3HT为给体材料，作为光敏活性层，通过溶液旋涂制备有机光电探测器件。
3.如权利要求2所述基于3-烷氧基-4-氰基噻吩的近红外有机光电分子材料的应用方法，其特征在于：所述有机光电探测器件为二极管型有机光电探测器件。
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