CN114957237B - 一种以烷基修饰的还原橙3为中心核的D(A-Ar)2型有机小分子的合成及应用 - Google Patents
一种以烷基修饰的还原橙3为中心核的D(A-Ar)2型有机小分子的合成及应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明属于有机光电材料技术领域,具体涉及一种以烷基链修饰的还原橙3为中心核的D(A‑Ar)2型结构有机小分子光电材料的合成及应用。是以染料还原橙3衍生物为给体单元(D),2,1,3‑苯并噻二唑衍生物为受体单元(A),并以碳二十长烷基链进行修饰。通过烷基化反应和Stille偶联反应,获得一种新给体核结构的有机小分子光伏材料。其以富勒烯PC71BM为受体的单层器件本体异质结太阳能电池的空穴迁移率和填充因子分别高达2.49×10‑4cm2V‑1s‑1和49.49%。本发明所涉及的发明材料具有良好的溶解性和稳定性,有望应用于有机太阳能电池给体材料以及空穴传输材料。
Description
技术领域
本发明涉及有机小分子光电领域,特别涉及了一种以烷基修饰的还原橙3为中心核的D(A-Ar)2型有机小分子的合成及应用。
技术背景
科学研究者合成了大量具有D(A-Ar)2骨架的小分子太阳能电池材料,并***研究了它们的光电性能。如分别以引达省二噻吩(IDT)[1]、二噻吩硅芴(DTS)[2]、苯并二噻吩(BDT)[3]和卟啉[4]等不同稠环核为中心给体单元的小分子太阳能电池(SMSCs)。这种设计策略可有效地解决小分子给体材料成膜质量差的科学问题,同时,有机小分子由于其主链结构的高效共轭以及端基受体单元与中心给体核之间的分子内存在电荷转移(ICT),而表现出较高的载流子迁移率和摩尔吸光系数。
多环芳香族化合物在光电领域的应用越来越受到人们的关注。主要是因为多环大π稠环核具有更大的π电子离域范围,刚性结构的大π稠环核的重组能较低,有利于获得较高的载流子迁移率[4-5]。之前就有相关同分异构体大稠环光电材料的报道[6-9]。但是已报道的大稠环合成步骤较为繁琐,合成成本高。基于上述考虑,为了获得平面性好且具有较高载流子迁移率的给体材料,于是我们以工业化低价染料多环大π稠环核还原橙3为起始原料制作中心给体核,并对其以碳二十的长烷基链进行修饰,以2,1,3-苯并噻二唑衍生物(BT)为受体单元,噻吩作为桥联单元,设计并合成了一种以大稠环为给体核的D(A-Ar)2型线型小分子给体材料,***研究了它们的分子结构对材料热稳定性以及光电性能的影响。
附:主要参考文献
[1]Liu D,Xiao M,Du Z,et al.Journal of Materials Chemistry C,2014,2(36):7523-7530.
[2]Sun Y,Seifter J,Huo L,et al.Advanced Energy Materials,2015,5(3):1400987.
[3]Lin Y,Ma L,Li Y,et al.Advanced Energy Materials,2013,3(9):1166-1170.
[4]Qin H,Li L,Guo F,et al.Energy&Environmental Science,2014,7(4):1397-1401.
[5]Liu B,Duan L,Chen J,et al.Dyes and Pigments,2017,139:42-49.
[6]Giguère J B,Verolet Q,Morin J F.Chemistry–A European Journal,2013,19(1):372-381.
[7]Matsuno T,Kamata S,Hitosugi S,et al.Chemical Science,2013,4(8):3179-3183.
[8]Giguère J B,Morin J F.The Journal of organic chemistry,2013,78(24):12769-12778.
[9]Giguère J B,Boismenu-Lavoie J,Morin J F.The Journal of organicchemistry,2014,79(6):2404-2418
发明内容
针对现有技术所存在的问题,我们发明了一种基于染料还原橙3衍生物为中心核的D(A-Ar)2型结构有机小分子光伏材料,该类材料的特点是以染料还原橙3衍生物为给体单元(D),2,1,3-苯并噻二唑衍生物为受体单元(A),并以联噻吩作为封端基团。利用这类D(A-Ar)2型结构有机小分子光伏材料,通过溶液加工,制作了有机小分子光伏器件(OSCs)。实现了以廉价的染料还原橙3为起始原料构筑成D(A-Ar)2型结构光伏材料的太阳能电池光电转换。
因此,本发明的目的在于提供一种价格低廉的,且具有一定光电转换能力的小分子光伏材料,该材料具有较好的成膜性;在与PC71BM共混的情况下,该类材料具有较好的光电转化效率。
本材料在经典D-A结构基础上,通过引入平面大稠环结构的AAN单元,旨在实现较大的电荷离域范围,提高载流子迁移率。其中以碳二十烷基链修饰的还原橙中心单元的设计与合成属于首创,发明的C20AAN单元以及小分子C20AAN-BT和C20AAN-DFBT有利于有机光伏供体材料的分子构筑及其在溶剂加工型本体异质结有机太阳能电池中的应用。这类D(A-Ar)2型结构材料的分子结构以及中间体可以是下列分子的任何一种。
式一:C20AAN
式二:C20AAN-T
式三:C20AAN-T-SnMe
式四:C20AAN-BT
式五:C20AAN-DFBT
上述D(A-Ar)2型有机小分子光伏材料,包括下面任何衍生物:
以4,10-二溴-6,12-二(2-辛基十二烷氧基)蒽并蒽(C20AAN)为推电子基团,以2,1,3-苯并噻二唑(BT)为拉电子基团的D(A-Ar)2型小分子光伏材料C20AAN-BT。
以4,10-二溴-6,12-二(2-辛基十二烷氧基)蒽并蒽(C20AAN)为推电子基团,以5,6-二氟-2,1,3-苯并噻二唑(DFBT)为拉电子基团的D(A-Ar)2型小分子光伏材料C20AAN-DFBT。
以下为具体合成路线:
为了得到上述材料,本发明的合成方案如下:
D(A-Ar)2型小分子光伏材料给体核C20AAN合成:还原橙3(Vat Orange 3)在氢氧化钠溶液,Aliquat 336和保险粉的作用下,在加热的条件下,与1-溴-2-辛基十二烷发生亲核取代反应,合成得到具有碳二十烷氧基侧链的C20AAN粗产品,经柱层析分离得到纯品。
D(A-Ar)2型小分子光伏材料给体核中间体C20AAN-T合成:4,10-二溴-6,12-二(2-辛基十二烷氧基)蒽并蒽在加热条件下,双三苯基磷二氯化钯催化下与噻吩丁基锡发生Stille偶联反应,合成得到C20AAN-T,经柱层析分离得到纯品。
D(A-Ar)2型小分子光伏材料给体核中间体C20AAN-T-SnMe合成:4,10-二(2-噻吩基)-6,12-二(2-辛基十二烷氧基)蒽并蒽在低温条件下,先与正丁基锂进行亲电取代反应,再与三甲基氯化锡发生亲核取代反应,合成得到C20AAN-T-SnMe,直接用于下一步反应。
D(A-Ar)2型小分子光伏材料目标分子C20AAN-BT的合成:侧链BT-T与给体核中间体C20AAN-T-SnMe在双三苯基磷二氯化钯催化下发生stille偶联反应,合成得到D(A-Ar)2型小分子光伏材料C20AAN-BT,粗产品经柱层析分离得到纯品。
D(A-Ar)2型小分子光伏材料目标分子C20AAN-DFBT的合成:侧链DFBT-T与给体核中间体C20AAN-T-SnMe在双三苯基磷二氯化钯催化下发生stille偶联反应,合成得到D(A-Ar)2型小分子光伏材料C20AAN-DFBT,粗产品经柱层析分离得到纯品。
本发明的D(A-Ar)2型小分子光伏材料与已公开的大多数小分子光电材料相比,其特点是:(1)由于中心核的起始原料为价格低廉的工业染料还原橙3,另一名称是C.I.颜料红168,因此设计的D(A-Ar)2型小分子材料制备成本更低,原料来源更加广泛;(2)并且引入长烷基碳二十烷基链(2-辛基十二烷基)进行修饰,使本身溶解性欠佳的2,1,3-苯并噻二唑(BT)类拉电子基团也能与大稠环进行连接;(3)噻吩桥的引入很好的拓宽了分子的吸收范围以及使小分子材料具有更强的分子间相互作用,更紧密的π-π堆积作用;(4)分子中给受体相互作用的存在,形成强的ICT作用,增强电荷传输性能。因此,这类材料是一类很有发展前景的有机小分子光电材料。
本发明的应用在于:将设计的光伏小分子材料作为给体,与PC71BM在不同比列下共混,制作光伏器件,实现将太阳能较好的转换为电能。
所述的有机小分子光伏器件包括氧化锡铟导电玻璃衬底层(ITO),阳极层。其中阳极修饰层为聚二氧乙基噻吩(PEDOT,30nm)涂层;阴极为Ca(10nm)/Al(100nm)的沉积层;活化层材料为本发明所述的D(A-Ar)2分子与PC71BM,其共混重量比为1:3。
附图说明
图1为本发明C20AAN-BT的热失重曲线图
图2为本发明C20AAN-BT与PC71BM的混合比例为1:3(w/w,12mg/mL)下的J-V曲线图
图3为本发明C20AAN-BT与PC71BM的混合比例为1:3(w/w,12mg/mL)下的EQE曲线图
图4为C20AAN-BT与PC71BM的混合比例为1:3(w/w,12mg/mL)时单电子器件的J1/2-V曲线
图5为本发明中材料的分子结构创新点
具体实施方式
下面通过具体实施例对本发明作进一步说明,但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
4,10-二溴-6,12-二(2-辛基十二烷氧基)蒽并蒽(C20AAN)的合成
氮气保护下,于500毫升单口瓶中装有还原橙3(2g,4.32mmol),氢氧化钠溶液(0.1M,200mL,20mmol),Aliquat 336(2.12g,2.4mL,5.24mmol),硫代硫酸钠(1.94g,11.12mmol),和1-溴-2-辛基十二烷(12.44g,34.48mmol).反应液加热到60℃反应5h,直到反应体系变成无色。将水轻轻倒出,然后加入甲醇120mL。将粗产品抽滤出来,然后用甲醇洗涤。用硅胶柱层析纯化(二氯甲烷/石油醚1:5v/v)得到化合物C20AAN为橙色固体(3.54g,80%).1H NMR(400MHz,CDCl3)δ8.75(d,J=10.7Hz,4H),8.61(d,J=7.5Hz,2H),8.18(t,J=7.9Hz,2H),4.19(d,J=5.2Hz,4H),2.26-2.05(m,2H),1.85(d,J=5.4Hz,4H),1.70(s,4H),1.54-1.10(m,56H),0.89(d,J=7.2Hz,12H).
实施例2
4,10-二(2-噻吩基)-6,12-二(2-辛基十二烷氧基)蒽并蒽的合成
氮气保护下,于100mL单口瓶中装有化合物C20AAN(1.027g,1mmol),2-三正丁基锡噻吩(783mg,2.1mmol),双三苯基磷二氯化钯(42mg,0.06mmol),以及干燥的甲苯(12mL).反应液加热到110℃反应过夜.反应停止并冷却后,用硅胶柱层析纯化(二氯甲烷/石油醚1:4v/v)得到化合物C20AAN-T为橙红色固体(930mg,90%).1H NMR(400MHz,CDCl3)δ8.83(d,J=8.1Hz,2H),8.69-8.56(m,4H),8.16(t,J=7.7Hz,2H),7.61-7.46(m,4H),7.38-7.29(m,2H),4.28(d,J=5.0Hz,4H),2.16(d,J=5.0Hz,2H),1.85(dd,J=13.4,6.7Hz,4H),1.68(dd,J=13.1,6.5Hz,4H),1.31(t,J=24.0Hz,56H),0.89(d,J=5.5Hz,12H).
实施例3
4,10-二(2-噻吩基)-6,12-二(2-辛基十二烷氧基)蒽并蒽-三甲基氯化锡的合成
在250mL三口瓶中,将化合物C20AAN-T(900mg,0.87mmol)溶于60mL干燥的四氢呋喃中,并加入四甲基乙二胺(404mg,3.48mmol),氮气保护下,磁力搅拌,-78℃下缓慢滴加正丁基锂(1.74mL,2.0M),-78℃下反应2h。然后一次性滴加三甲基氯化锡(5.22mL,5.22mmol,1M),室温反应12h。将反应液倒入100mL水中,二氯甲烷萃取三次,每次30mL,合并有机层用饱和盐水洗涤三次,每次50mL。将有机层减压旋干,真空干燥,得到橙红色固体C20AAN-T-SnMe(1.17g,99%)。1H NMR(400MHz,CDCl3)δ8.82(d,J=7.8Hz,2H),8.66(d,J=7.3Hz,2H),8.60(s,2H),8.15(s,2H),7.67(s,2H),7.38(s,2H),4.27(s,4H),2.17(d,J=4.8Hz,2H),1.84(s,4H),1.68(s,4H),1.28(s,56H),0.88(d,J=4.0Hz,12H),0.49(s,18H).
实施例4
C20AAN-BT的合成
化合物BT-T(72mg,0.147mmol)和4,10-二(2-噻吩基)-6,12-二(2-辛基十二烷氧基)蒽并蒽-三甲基氯化锡(C20AAN-T-SnMe)(95mg,0.07mmol)溶解于10mL甲苯中,反应体系反复排氧和抽取氮气三次.双三苯基磷二氯化钯(3mg,0.0042mmol)加到反应体系中,体系在110℃下反应12h。反应停止后,减压旋蒸出溶剂.使用洗脱剂为(石油醚/二氯甲烷体=1:1)的混合溶液柱层析纯化,获得到暗红色的固体产物C20AAN-BT(110mg,yield:85%)。1HNMR(400MHz,CDCl3)δ8.62(d,J=7.2Hz,2H),8.57(s,4H),8.29(s,2H),7.95(s,4H),7.78(d,J=7.3Hz,2H),7.66(d,J=7.3Hz,2H),7.58(s,2H),7.13(s,2H),7.08(s,2H),6.71(s,2H),4.23(s,4H),2.82(t,J=6.8Hz,4H),2.14(d,J=3.2Hz,2H),1.92(s,4H),1.72(s,10H),1.47-1.06(m,64H),0.90(t,6H),0.83(t,12H).
实施例5
C20AAN-DFBT的合成
化合物DFBT-T(78mg,0.147mmol)和4,10-二(2-噻吩基)-6,12-二(2-辛基十二烷氧基)蒽并蒽-三甲基氯化锡(C20AAN-T-SnMe)(95mg,0.07mmol)溶解于10mL甲苯中,反应体系反复排氧和抽取氮气三次.双三苯基磷二氯化钯(3mg,0.0042mmol)加到反应体系中,体系在110℃下反应12h。反应停止后,减压旋蒸出溶剂.使用洗脱剂为(石油醚/二氯甲烷体=1:1)的混合溶液柱层析纯化,获得到暗红色的固体产物C20AAN-DFBT(143mg,yield:83%)。1H NMR(400MHz,CDCl3)δ8.85(d,J=8.0Hz,2H),8.78(s,2H),8.73(s,2H),8.64(s,2H),8.21(d,J=13.4Hz,4H),7.51(s,2H),7.31(s,4H),7.02(s,2H),4.29(d,J=12.5Hz,4H),2.91(s,4H),2.16(s,2H),1.93(s,2H),1.81(s,4H),1.74(s,8H),1.57-1.10(m,64H),0.98(d,J=21.1Hz,6H),0.93(dd,J=17.8,11.1Hz,12H).
实施例6
D(A-Ar)2型小分子光伏材料的性能表征及其光伏光器件的制作和发光性能的测试
D(A-Ar)2型小分子光伏材料的1H NMR光谱通过Bruker Dex-400 NMR仪器测定,紫外-可见吸收光谱通过HP-8453紫外-可见光谱仪测定,荧光光谱通过HITACHI-850荧光光谱仪测定。
基于D(A-Ar)2型小分子材料的光伏器件包括:氧化锡铟(ITO)导电玻璃阳极层、聚二氧乙基噻吩(PEDOT)阳极修饰层。活化层层由所述小分子材料和PC71BM共混构成,其共混比列为1:2。阴极由Ca(10nm)/Al(100nm)层构成。
实施例7
C20AAN-BT热稳定性能及其小分子光伏器件性能
C20AAN-BT的热失重曲线图如图1所示。其分解温度为363℃。
C20AAN-BT与PC71BM的混合比例为1:3(w/w,12mg/mL)下的J-V曲线图如图2所示。在该条件下,器件的短路电流为2.22mA/cm2,开路电压为0.77V,填充因子为49.49%,光伏效率为0.85%。
C20AAN-BT与PC71BM的混合比例为1:3(w/w,12mg/mL)下EQE曲线图如图3所示。该图显示的EQE测试范围为300-800nm,在368nm处有最大EQE值,为8.77%。
C20AAN-BT与PC71BM的混合比例为1:3(w/w,12mg/mL)时单电子器件的J1/2-V曲线如图4所示,其空穴迁移率最大为2.49×10-4cm2 V-1s-1。
尽管结合了优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解所附权利要求概括了本发明的范围。在本发明构思的指导下,本领域的技术人员应当意识到,对本发明的各实施例方案所进行的一定的改变,都将被本发明的权利要求书的精神和范围所覆盖。
Claims (4)
1.一种以碳二十长烷基修饰的还原橙3为中心核的D(A-Ar)2型结构有机小分子光伏材料,其特征在于选自如下化合物中的一种:
2.根据权利要求1所述的一种以碳二十长烷基修饰的还原橙3为中心核的D(A-Ar)2型结构有机小分子光伏材料在用于实现小分子光伏器件的能量转换中的用途,其特征在于,将所述的D(A-Ar)2型结构有机小分子光伏材料与PC71BM共混作为光伏器件的活性层。
3.根据权利要求2所述的材料的用途,其特征在于,所述的一种以碳二十长烷基修饰的还原橙3为中心核的D(A-Ar)2型结构有机小分子光伏材料与PC71BM共混质量比为1:3。
4.根据权利要求2所述材料的用途,其特征在于,所述的一种以碳二十长烷基修饰的还原橙3为中心核的D(A-Ar)2型结构有机小分子光伏材料的小分子光伏器件的阳极修饰层为聚二氧乙基噻吩(PEDOT)涂层。
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