CN103524481B - 用于太阳能电池应用的低带隙的二氰基乙烯基和三氰基乙烯基低聚噻吩 - Google Patents
用于太阳能电池应用的低带隙的二氰基乙烯基和三氰基乙烯基低聚噻吩 Download PDFInfo
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- CN103524481B CN103524481B CN201310269977.9A CN201310269977A CN103524481B CN 103524481 B CN103524481 B CN 103524481B CN 201310269977 A CN201310269977 A CN 201310269977A CN 103524481 B CN103524481 B CN 103524481B
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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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
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
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- H—ELECTRICITY
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Abstract
本发明涉及一种用于使用在太阳能电池应用中的可溶液处理的、p型、低光隙的低聚物噻吩化合物,含有至少一种含噻吩的基团、至少一种吸电子的二氰基乙烯基或三氰基乙烯基基团以及至少一种供电子的二苯基氨基芴基或N-烷基咔唑基团。
Description
技术领域
本发明涉及一种用于太阳能电池应用的合成化合物。具体但不唯一地,本发明还涉及一种用于太阳能电池应用的低聚噻吩化合物。
背景技术
化石燃料仍是今天的主要能源。诸如煤、石油和天然气的化石燃料的示例是需要成千上万年形成的且开采昂贵的不可再生的天然来源。此外,燃烧化石燃料产生大量的二氧化碳以及不期望的空气污染物。为了解决这些,一直在广泛研究和调查清洁且可再生的能源诸如太阳能,太阳能可以直接被捕集并通过太阳能电池转化成电能。例如,已经采用光伏(PV)技术来制备不同类型的太阳能电池,诸如晶体硅太阳能电池、无定形硅太阳能电池、染料敏化太阳能电池、铜铟镓硒化物(CIGS)太阳能电池以及有机太阳能电池等。
在由不同的PV技术制造的太阳能电池中,已知有机太阳能电池具有制造成本低且工艺灵活性高的优势。具体地,无论从学术界,还是从业内,有机太阳能电池诸如本体异质结(BHJ)光伏(PV)器件因其相对低的成本、轻的重量、易于通过溶液工艺大面积制造以及与柔性衬底的相容性而作为有希望的可再生能源替代品已经引起了相当大的关注。
发明内容
本发明的目的是为了一种使用在太阳能电池应用中的化合物。
根据本发明,提供了一种使用在太阳能电池应用中的化合物,该化合物含有:
至少一种含噻吩的基团;
至少一种吸电子基团,含有至少一种氰基乙烯基基团;以及
至少一种供电子基团;
其中,所述至少一种供电子基团选自由二苯基氨基芴基或N-烷基咔唑基团及其混合物所组成的组中。
在此方面的实施方案中,至少一种氰基乙烯基选自由二氰基乙烯基、三氰基乙烯基及其混合物所组成的组中。
在此方面的实施方案中,该化合物具有式I所示的结构:
(式I),
其中,n选自2到3的范围。
在此方面的实施方案中,该化合物具有式II所示的结构:
(式II)。
在此方面的实施方案中,该化合物具有式III所示的结构:
(式III),
其中,n选自1到2的范围。
在此方面的实施方案中,该化合物具有式IV所示的结构:
(式IV),
其中,n选自1到2的范围。
在此方面的实施方案中,该化合物具有式V所示的结构:
(式V)。
附图说明
图1显示了根据本发明的基于三氰基乙烯基的低聚噻吩化合物的在薄膜中测量的吸收光谱。
图2显示了根据本发明的基于二氰基乙烯基的低聚噻吩化合物的在薄膜中测量的吸收光谱。
具体实施方式
不希望受到理论的束缚,本发明通过试验、研究、学习以及检验结果和观察结果得出下述意见:应用低聚噻吩化合物用于BHJ太阳能电池具有有益效果。通过改进材料性能、制造技术以及器件结构,最近基于与可溶性富勒烯衍生物诸如[6,6]-苯基C61-丁酸甲酯(PCBM)共混的可溶液处理的p型共轭半导体材料的BHJ PV电池的功率转换效率(PCE)已经达到高于8-9%(Z.He,C.zhong,S.Su,M.Xu,H Zhong,S.Su,M.Xu,H.Wu,Y.Cao,Nat.Photon.2012,6,591;X.Li,W.C.H.Choy,L.Huo,F.Xie,W.E.I.Sha,B.Ding,X.Guo,Y.Li,J.Hou,J.You,Y.Yang,Adv.Mater.2012,24,3046;J.You,L.Dou,K.Yoshimura,T.Kato,K.Ohya,T.Moriarty,K.Emery,C.-C.Chen,J.Gao,G.Li,Y.Yang,Nat.Common.2013,4,1446;L.Dou,J.You,J.Yang,C.-C.Chen,Y.He,S.Murase,T.Moriarty,K.Emery,G.Li,Y.Yang,Nat.Photon.2012,6,180;T.-Y.Chu,J.Lo,S.Beaupre,Y.Zhang,J.-R.Pouliot,J.Zhou,A.Najari,M.Leclerc,Y,Adv.Funct.Mater.2012,22,2345)。除了聚合物外,已经发现π-共轭的小分子作为可替代的可溶液处理的p型供体材料是有吸引力的,因为单分散性、易于获得高纯度和可再现性特性。因此,使用可溶液处理的小分子用于PV应用也引起了相当大的关注。同时,基于可溶液处理的小分子有机薄膜太阳能电池也显著改进,近来效率超过7%(J.Zhou,X.Wan,Y.Liu,Y.Zuo,Z.Li,G.He,G.Long,W.Ni,C.Li,X.-C.Su,Y.Chen,J.Am.Chem.Soc.2012,134,16345;Y.Sun,G.C.WelchW.L.Leong,C.J.Takacs,G.C.Bazan,A.J.Heeger,Nat.Mater.2011,11,44;A.Mishra,P.Bauerle,Anew.Chem.Int.Ed.2012,51,2020;R.Fitzner,E.Mena-Osteritz,A.Mishra,G.Schulz,E.Remold,M.Weil,C.Korner,H.Ziehlke,C.Elschner,K.Leo,M.Riede,M.Pfeiffer,C.Uhrich,P.Bauerle,J.Am.Chem.Soc.2012,134,11064;T.S.van der Poll,J.A.Love,T.-Q.Nguyen,G.C.Bazan,Adv.Mater.2012,24,3646)。然而,更有效且稳定的器件仍将需要进一步开发极佳的材料以及可以在商业化之前实现处理和器件优化。在限制异质结PV电池的PCE的诸多因素中,有机半导体材料较低的光能利用效率和低的载荷传输效率是最具决定性的因素。因此,开发具有宽的吸收和窄的带隙以及高载荷子迁移率的新的p型有机/聚合物半导体是获得高效的有机PV电池的先决条件。
使用分子内电荷转移从富电子单元到贫电子单元已经成为获得低带隙分子/聚合物***的有希望的方法。此外,选择富电子和/或贫电子部分提供了一种合适地控制供体和受体材料的前线分子轨道的位置的方式,这对实现异质结处有效的激发离解并获得太阳能电池的大的开路电压(Voc)是不可或缺的且还直接涉及半导体材料的光子氧化稳定性。
发明人先前的基于这些作为供体材料的基于三氰基乙烯基生色团和作为受体材料的C60的双层异质结PV电池的研究显示出在退火器件中高达1.33%的PCE和0.82V的大的开路电压。
在另一项尝试中,由与作为受体的PCBM共混的不对称封端有溶解的三芳基胺或三芳基氨基取代的咔唑树枝状大分子和二氰基乙烯基的五噻吩和六噻吩制造的溶液处理的本体异质结PV电池显示出这样制造的器件中高达1.72%的PCE且Voc=0.79V。此外,由与作为受体的PC71BM共混的二氰基乙烯基取代的树枝状大分子制造的本体异质结PV电池显示出在退火器件中高达1.64%的功率转换效率且开路电压(Voc)=0.93V。
在本发明中,体现了用于使用在太阳能电池应用中的若干种新的可溶液处理的、p型以及低光隙低聚噻吩化合物的设计和合成。具体地,化合物包括至少一种含噻吩的基团、包含至少一种氰基乙烯基基团的至少一种吸电子基团;以及至少一种供电子基团;其中所述至少一种供电子基团选自由二苯基氨基芴基或N-烷基咔唑基团及其混合物组成的组。
优选地,至少一个氰基乙烯基选自由二氰基乙烯基、三氰基乙烯基及其混合物组成的组。下面显示了许多所体现的化合物的结构和制备过程。
实验过程
实施例1
化合物1(PhN-OF(2)OT(n)-TCN)。
实施例1体现了含低聚噻吩的化合物(化合物1,PhN-OF(2)OT(2)-TCN和PhN-OF(2)OT(3)-TCN),包括作为供电子基团的二苯基氨基-双芴基和作为吸电子基团的三氰基乙烯基,其中n个噻吩基团选自2到3的范围内。
化合物1的合成概括在方案1中。在碱性条件下,2,7-二溴芴以高收率(92%)被转化成双烷基化产物9,9-双-(正丁基)-2,7-二溴芴1。在将1Buchwald-Hartwig氨化之后,2通过锂化,然后与三甲基硼酸酯反应,接着水解被转化成硼酸3。硼酸3与9,9-双-(正丁基)-2,7-二溴芴1进行Suzuki交叉偶联反应而以良好的收率得到PhN-OF(2)-Br4,其随后使用类似的方法被转化成硼酸,R2-B(OH)2。R2-B(OH)2与5-碘-2,2’-并噻吩的铂催化的Suzuki交叉偶联反应(J.Phys.Chem.C2008,112,16714-16720)以86%的收率得到了黄色固体的关键的中间体5a,该中间体随后与n-BuLi和四氰基乙烯反应,以高收率得到产物,PhN-OF(2)OT(2)-TCN。以类似的方式,采用相同的反应顺序合成扩展的中间体5b,该中间体5b随后以良好的收率转化成第二目标分子PhN-OF(2)OT(3)-TCN。
试剂和条件:a)n-C4H9Br、KOH、DMF,90℃,过夜,80%;b)二苯基胺,NaOBu-t,甲苯,110℃,24h,76%;c)(i)n-BuLi,THF,-78℃,1h;(ii)B(OCH3)3,-78℃至室温,2h,79%;d)Pd(PPh3)4,2M K2CO3,80℃,62%;e)(i)n-BuLi,THF,-78℃,1h;(ii)B(OCH3)3,-78℃至室温,2h,72%;f)Pd(PPh3)4,2M K2CO3,THF,5a(n=2),76%;5b(n=3),75%;g)1)n-BuLi2)四氰基乙烯,PhN-OF(2)OT(2)-TCN,90%;PhN-OF(2)OT(3)-TCN,79%。
方案1PhN-OF(2)OT(n)-TCN(n=2-3)的合成途径
实施例2
化合物2(PhN-OFFT-TCN)。
实施例2体现了含低聚噻吩的化合物(化合物2,PhN-OFFT-TCN),包括作为供电子基团的二苯基氨基芴基和作为吸电子基团的三氰基乙烯基。
方案2显示了化合物2被合成。在酸性条件下,二噻吩并[3,2-b:2’3’-d]噻吩(Organic Syntheses,第83卷,第209页(2006))与NBS反应,得到2-溴二噻吩并[3,2-b:2’3’-d]噻吩7,其与硼酸R1-B(OH)2进行Suzuki交叉偶联反应(J.Mater.Chem.,2010,20,2182-2189)以便以72%的收率得到中间体8。最终,8通过在低温下与n-BuLi和四氰基乙烯反应而以85%的收率被转化成PhN-OFFT-TCN。
试剂和条件:a)NBS、CHCl3/AcOH,74%;b)5-4,Pd(PPh3)4,2M K2CO3,THF,71%;c)1)n-BuLi,2)四氰基乙烯,85%。
方案2PhN-OFFT-TCN的合成途径
实施例3
化合物3-1(ADDA-1) 化合物3-2(ADDA-2)
实施例3体现了含低聚噻吩的化合物(化合物3-1,ADDA-1和化合物3-2,ADDA-2),每一种包括作为供电子基团的两个二苯基氨基芴基和作为吸电子基团的两个二氰基乙烯基,其中每一个芴基的n独立地选自1到2的范围内。
化合物3-1和化合物3-2的结构设计是基于缠绕的二噻吩骨架,由于空间效应(J.Adv.Funct.Mater.2007,17,1163)。在二噻吩的3-和3’位引入大体积基团能够在噻吩环之间产生二面角,因而产生用于构建这些化合物的非平面的核。
方案3概括了ADDA-1(n=1)和ADDA-2(n=2)的合成途径。新制备的在干四氢呋喃(THF)中的2-溴噻吩的格氏试剂与2-溴噻吩的钯催化的Kumada偶联反应以高收率得到二噻吩9。在酸性条件下用溴(Br2)过度溴化二噻吩以78%的收率得到了3,3’,5,5’-四溴-2,2’-二噻吩10。使用在含水盐水(HCl)中的Zn/AcOH还原10以高收率得到了无色晶体的期望的3,3’-二溴-2,2’-二噻吩11。芳基硼酸R1-B(OH)2或R2-B(OH)2与3,3’-二溴-2,2’-二噻吩的钯催化的Suzuki交叉偶联反应分别得到了相应的“双供体”中间体12a或12b。在先前使用的典型的方案之后,供体取代的中间体12a以良好的收率被转化成二硼酸13a。无需进一步纯化,13a与碘-四噻吩甲醛进行Suzuki交叉偶联以良好的收率得到了相应的期望的供体取代的低聚噻吩14a。最后,14a通过在氮气(N2)下,在氯仿(CHCl3)中的吡啶存在下与丙二腈反应被转化成ADDA(n=1)。根据类似的过程还制备了ADDA(n=2)。
试剂和条件:a)Br2、CHCl3/AcOH,76%;b)Zn,AcOH,3M HCl,C2H5OH,H2O,95%;c)Pd(PPh3)4,2M K2CO3,THF,12a,71%;12b,70%;d)1)n-BuLi,2)B(OCH3)3,13a,70%;13b,68%;e)Pd(PPh3)4,2M K2CO3,THF,14a,68%;14b,73%;f)丙二睛,吡啶,CHCl3,过夜,ADDA-1,93%;ADDA-2,90%。
方案3ADDA-1和ADDA-2的合成途径
实施例4
化合物4(ADDA-3)。
实施例4体现了含低聚噻吩的化合物(化合物4,ADDA-3),包括作为供电子基团的两个N-烷基咔唑基团和作为吸电子基团的两个二氰基乙烯基。
根据方案4合成ADDA-3。
试剂和条件:a)n-C10H21,50%NaOH,苯,90%;b)NBS,CH2Cl2,87%;c)n-BuLi,2)B(OCH3)3,80%;d)Pd(PPh3)4,2M K2CO3,THF,75%;e)1)n-BuLi,2)B(OCH3)3,72%;f)Pd(PPh3)4,2M K2CO3,THF,73%;g)丙二睛,吡啶,CHCl3,过夜,ADDA-3,95%。
方案4ADDA-3的合成途径
表征和结果
通过1H NMR、13C NMR、HRMS充分表征所有新合成的低聚噻吩且发现与预期的结构吻合良好。
9,9-双-(正丁基)-2,7-二溴芴(1)。在N2下,将12.0g(37mmol)的2,7-二溴芴2-7、12mL(111mmol)的1-溴丁烷、6.3g(1mmol)的氢氧化钾、0.9g(6mmol)的碘化钾、0.29g(1mmol)的18-冠-6以及120mL的DMF的混合物搅拌并加热至90℃过夜。在冷却至室温后,将溶液倾倒至冷水并用二氯甲烷萃取(3×50mL)。用水洗涤合并的有机层,通过无水Na2SO4干燥,过滤并蒸发至干燥。通过硅胶色谱柱使用石油醚作为洗脱剂来纯化粗产物,得到了白色固体的期望产物(12.9g,80%)。Mp:116.8-118.5℃。1H NMR(400MHz,CDCl3,δ)7.53(d,J=8.8Hz,2H),7.46(dd,J=7.2Hz,J=2.2Hz,4H),1.90-1.94(m,4H),1.06-1.11(m,4H),0.70(t,J=7.4Hz,3H),0.54-0.59(m,4H).13C NMR(100MHz,CDCl3,δ)152.5,139.1,130.2,126.2,121.5,121.2,55.6,40.1,25.8,22.9,13.8.MS(FAB)m/z436.1(M+)。
9,9-双(正丁基)-7-溴-2-二苯基氨基芴(2)。向双颈圆底烧瓶中添加1.69g(10mmol)的二苯基胺、4.36g(10mmol)的9,9-双(正丁基)-2,7-二溴芴1、100mg(0.5mmol)的Pd(OAc)2、250mg(1mmol)的P(邻甲苯)3、3.0g(30mmol)的NaOBu-t以及80mL的甲苯。在N2下,搅拌混合物并加热至110℃持续36小时。在冷却至室温后,将溶液倾倒至冷水并用乙酸乙酯萃取(3×80mL)。用水洗涤合并的有机层,通过无水硫酸钠干燥,过滤并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了白色固体的期望产物(3.95g,76%)。Mp:116.0-118.0℃。1H NMR(400MHz,CDCl3,δ)7.40-7.52(m,4H),7.22-7.27(m,4H),7.08-7.13(m,5H),6.99-7.03(m,3H)1.80-1.85(m,4H),1.02-1.08(m,4H),0.70(t,J=7.4Hz,6H),0.59-0.67(m,4H).13C NMR(100MHz,CDCl3,δ)152.8,151.7,147.8,147.5,139.9,134.9,129.9,129.2,125.9,123.9,123.3,122.6,120.4,120.3,120.1,118.9,55.2,39.9,25.9,22.9,13.9.MS(FAB)m/z524.4(M++1)。
9,9-双(正丁基)-2-二苯基氨基-7-芴基硼酸(3)。在N2下,在-78℃下向含有1.3g(2.47mmol)的化合物2和30mL的干THF中逐滴添加2.3mL(3.71mmol)的1.6M的正丁基锂,同时保持良好的搅拌。搅拌1小时后,在一部分中添加硼酸三甲酯(0.4mL,3.71mmol)。然后在-78℃下搅拌混合物1小时。当混合物自然升温至-30℃时,添加水和HCl(3M)。接着,将反应混合物倾倒入用乙酸乙酯(3×50mL)萃取的水团块中。用无水硫酸钠干燥合并的有机层,过滤并在35℃下蒸发至干燥。通过硅胶色谱柱使用二氯甲烷和石油醚/乙酸乙酯作为洗脱剂来纯化粗产物,得到了浅黄色固体(0.96g,79%)。1H NMR(400MHz,DMSO-d6,δ)8.02(s,2H),7.80(s,1H),7.77(d,J=7.6Hz,1H),7.71(d,J=8.4Hz,1H),7.27(t,J=7.6Hz,1H),7.08(d,J=1.6Hz,1H),6.93-7.01(m,6H),6.91(d,J=2.0Hz,1H),1.79-1.88(m,4H),0.95-1.04(m,4H),0.65(t,J=7.4Hz,6H),0.50-0.58(m,4H).13C NMR(100MHz,DMSO-d6,δ)152.1,148.9,147.4,146,8,142.1,136.1,133.1,129.4,129.3,128.2,123,3,122.7,121.1,119.1,118.3,54.3,39.2,25.8,22.4,13.8.MS(FAB)m/z489.7(M+)。
PhN-OF(2)-Br(4)。向100mL的圆底烧瓶中添加250mg(0.51mmol)的硼酸3、300mg(0.69mmol)的9,9-双-(正丁基)-2,7-二溴芴1、50mg的Pd(PPh3)4、4mL的2M K2CO3、5mL的甲苯以及8mL的CH3OH。在N2下,将混合物搅拌并加热至80℃过夜。在冷却至室温后,将反应混合物倾倒入水中并用二氯甲烷萃取(3×20mL)。通过无水硫酸钠干燥合并的有机层,过滤并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了略微黄色固体的期望产物(253mg,62%)。MP:186.0-188.0℃。1H NMR(400MHz,CDCl3,δ)7.58-7.70(m,8H),7.23-7.38(m,6H),7.13-7.15(m,5H),6.99-7.05(m,3H).13C NMR(100MHz,CDCl3,δ)152.4,151.4,151.3,150.9,147.9,147.1,140.8,140.4,140.1,139.6,135.9,129.1,126.9,126.8,125.9,125.8,123.8,123.5,122.9,122.5,121.2,120.4,119.9,119.7,119.4,119.3,55.1,40.2,39.9,26.1,25.9,23.1,23.0,13.9,13.8.MS(MALDI-TOF):m/z801.8(M+)。
PhN-OF(2)OT(2)(5a)。向100双颈圆底烧瓶中添加[R3-B(OH)2](460mg,0.6mmol)、5-碘-2,2’-二噻吩(2-5)(147mg,0.5mmol)、Pd(PPh3)4(20mg)、THF(20mL)以及2M K2CO3(1.2mL)。在N2下,将溶液混合物加热至80℃过夜。在冷却至室温后,将反应混合物倾倒水中并用二氯甲烷萃取(3×30mL)。通过无水Na2SO4干燥合并的有机层,并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了黄色固体的期望产物(336mg,76%)。1H NMR(400MHz,CDCl3,δ)7.78-7.57(m,10H),7.32(d,J=3.6Hz,1H),7.28-7.22(m,6H),7.19(d,J=3.6Hz,1H),7.16-7.13(m,5H),7.06-6.99(m,4H),2.09-1.86(m,8H),1.16-1.08(m,8H),0.75-0.68(m,20H).13C NMR(100MHz,CDCl3,δ)152.4,151.8,151.6,151.4,147.9,147.1,143.9,140.6,140.2,139.7,139.5,137.5,136.3,135.9,132.7,129.1,127.9,126.0,125.9,124.6,124.5,124.3,123.8,123.5,123.4,122.5,121.2,121.1,120.4,120.1,119.9,119.8,119.3,55.2,55.1,40.3,39.9,26.1,26.0,23.1,23.0,13.9,13.8.MS(MALDI-TOF):m/z885.7902(M+)。
PhN-OF(2)OT(3)(5b)。使用硼酸[R2-B(OH)2](380mg,0.5mmol)、5-碘-2,2’:5’,2”-四噻吩(150mg,0.4mmol)、Pd(PPh3)4(20mg)、THF(20mL)以及2M K2CO3(1.0mL)来按照5a的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了无色固体的期望产物(290mg,75%)。1H NMR(400MHz,CDCl3,δ)7.78-7.57(m,10H),7.32(d,J=3.6Hz,1H),7.28-7.21(m,6H),7.19-7.17(m,2H),7.16-7.10(m,7H),7.06-6.99(m,4H),2.10-1.86(m,8H),1.16-1.06(m,8H),0.75-0.68(m,20H).13C NMR(100MHz,CDCl3,δ)152.4,151.8,151.6,151.4,147.9,147.1,144.0,140.6,140.5,140.2,139.6,139.5,137.1,136.3,136.1,135.9,135.8,132.6,129.1,126.1,125.9,124.6,124.5,124.4,124.1,123.8,123.7,123.6,123.5,122.5,121.2,121.1,120.4,120.1,119.9,119.8,119.3,55.2,55.1,40.3,39.9,26.1,26.0,23.1,23.0,13.9,13.8.MS(MALDI-TOF):m/z996.8428(M+)。
PhN-OF(2)OT(2)-TCN。在N2下,在-78℃下向含有5a(284mg,0.32mmol)和干THF(20mL)的干50mL双颈烧瓶中逐滴添加1.6M的正丁基锂(0.4mL,0.64mmol),同时保持良好搅拌。在-78℃下搅拌2小时后,在一部分中添加四氰基乙烯(128mg,1.0mmol),然后在-78℃下搅拌混合物0.5小时并升温至室温。然后用H2O猝灭反应混合物并倾倒入水中,用二氯甲烷(2×100mL)萃取。用无水硫酸钠干燥合并的有机相并蒸发至干燥。接着将粗产物加载到硅胶柱上并用石油醚/二氯甲烷洗脱,得到黑色的固体,该固体通过用CHCl3/CH3OH沉淀,用甲醇洗涤然后真空干燥来进一步纯化,得到了蓝黑色固体的期望产物(284mg,90%)。1H NMR(400MHz,CDCl3,δ)8.04(d,J=4.8Hz,1H),7.81(dd,J=9.4Hz,J=7.8Hz,2H),7.72-7.57(m,9H),7.47(d,J=4.0Hz,1H),7.42(d,J=4.4Hz,1H),7.29-7.25(m,4H),7.17-7.14(m,5H),7.07-7.01(m,3H),2.13-1.89(m,8H),1.18-1.09(m,8H),0.76-0.70(m,20H).13C NMR(100MHz,CDCl3,δ)152.6,152.4,152.2,151.8,151.5,150.9,147.9,147.2,142.3,141.7,141.3,140.4,139.3,139.2,135.8,132.9,131.9,131.6,131.3,130.1,129.2,126.3,126.0,125.2,125.0,124.9,123.9,123.5,122.5,121.3,121.2,120.4,120.3,120.2,119.4,119.3,112.8,112.7,112.3,80.7,55.4,55.1,40.2,39.9,26.1,26.0,23.03,23.01,13.9,13.8.HRMS(MALDI-TOF):计算:对于C67H62N4S2:986.4410;Found:986.4448。
PhN-OF(2)OT(3)-TCN。使用5b(242mg,0.25mmol),1.6M的正丁基锂(0.4mL,0.64mmol)、四氰基乙烯(128mg,1.0mmol)以及干THF(20mL)来按照PhN-OF(2)OT(2)-TCN的合成过程。接着将粗产物加载到硅胶柱上并用石油醚/二氯甲烷洗脱,得到黑色的固体,该固体通过用CHCl3/CH3OH沉淀,用甲醇洗涤然后真空干燥来进一步纯化,得到了蓝黑色固体的期望产物(210mg,79%)。1H NMR(400MHz,CDCl3,δ)8.02(d,J=4.4Hz,1H),7.80(dd,J=9.4Hz,J=7.8Hz,2H),7.72-7.60(m,8H),7.50(d,J=4.0Hz,1H),7.38(d,J=3.6Hz,1H),7.36(d,J=4.4Hz,1H),7.33(d,J=4.0Hz,1H),7.29-7.25(m,5H),7.17-7.14(m,5H),7.07-7.00(m,3H),2.12-1.87(m,8H),1.18-1.09(m,8H),0.76-0.70(m,20H).13C NMR(100MHz,CDCl3,δ)152.4,152.0,151.7,151.4,147.9,147.2,146.7,143.1,141.6,141.4,140.9,140.3,139.40,139.37,135.8,134.4,132.5,132.0,131.9,131.4,130.0,129.2,126.6,126.2,126.0,125.1,125.0,124.8,124.0,123.8,123.5,122.5,121.3,121.2,120.4,120.3,120.1,119.9,119.3,112.7,112.6,112.3,80.8,55.3,55.1,40.2,39.9,26.1,26.0,23.1,23.0,13.9,13.8.HRMS(MALDI-TOF):计算:对于C71H64N4S3:1068.4287;Found:1068.4245。
2-溴二噻吩[3,2-b:2’,3’-d]噻吩(7)。在0℃下,向6[2](196mg,1.0mmol)和AcOH(20mL)/CHCl3(20mL)的混合物中部分添加N-溴琥珀酰胺(178mg,1.0mmol)。搅拌混合物过夜,然后倾倒入H2O(150mL)中并用二氯甲烷萃取(3×30mL)。用盐水洗涤合并的有机萃取液,然后通过无水Na2SO4干燥。去除溶剂后,通过硅胶色谱柱使用石油醚作为洗脱剂来纯化残余物,得到无色液体的期望产物(203mg,74%)。1H NMR(400MHz,CDCl3,δ)7.38(d,J=5.2Hz,1H),7.29-7.27(m,2H).13C NMR(100MHz,CDC13,8)140.7,139.8,131,130.7,126.2,123.4,120.6,111.9.MS(FAB):m/z(M+)。
PhN-OFFT(8)。向100mL的双颈圆底烧瓶中添加[R1-B(OH)2]3(330mg,0.5mmol)、7(110mg,0.4mmol)、Pd(PPh3)4(20mg)、THF(30mL)以及2M K2CO3(1.0mL)。在N2下,将溶液混合物加热至80℃过夜。在冷却至室温后,将反应混合物倾倒水中并用二氯甲烷萃取(3×50mL)。通过无水Na2SO4干燥合并的有机相,并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了黄色液体的期望产物(230mg,71%)。1H NMR(400MHz,CDCl3,δ)7.65-7.56(m,SH),7.38(d,J=5.2Hz,1H),7.32(d,J=5.2Hz,1H),7.29-7.25(m,4H),7.16-7.13(m,SH),7.05-7.01(m,3H),1.97-1.82(m,4H),1.19-1.08(m,28H),0.87(t,J=6.8Hz,6H),0.73-0.69(m,4H).13C NMR(100MHz,CDCl3,δ)152.3,151.6,147.9,147.3,145.9,142.2,140.96,140.91,135.5,132.5,131.2,129.6,129.2,125.8,124.7,123.9,123.5,122.6,120.8,120.5,119.7,119.6,119.2,116.1,55.1,40.2,31.9,29.9,29.6,29.5,29.3,23.8,22.6,14.1.MS(MALDI-TOF):m/z806.7590(M+)。
PhN-OFFT-TCN。使用8(200mg,0.25mmol)、1.6M的正丁基锂(0.4mL,0.64mmol)、四氰基乙烯(128mg,1.0mmol)和干THF(20mL),按照PhN-OF(2)OT(2)-TCN的合成过程。接着将粗产物加载到硅胶柱上并用石油醚/二氯甲烷洗脱,得到黑色的固体,该固体通过用CHCl3/CH3OH沉淀,用甲醇洗涤然后真空干燥来进一步纯化,得到了蓝黑色固体的期望产物(193mg,85%)。1H NMR(400MHz,CDCl3,δ)8.27(s,1H),7.68-7.63(m,3H),7.59-7.57(m,2H),7.29-7.25(m,4H),7.16-7.07(m,SH),7.07-7.03(m,3H),1.98-1.83(m,4H),1.25-1.08(m,28H),0.85(t,J=6.8Hz,6H),0.71-0.68(m,4H).13C NMR(100MHz,CDCl3,δ)155.2,152.6,151.9,151.6,148.1,147.8,143.1,142.6,142.4,134.7,133.9,132.6,131.9,130.8,129.2,128.7,125.5,124.2,123.2,122.9,120.2,119.8,118.6,116.3,112.9,112.8,112.4,79.8,55.3,40.2,31.9,29.9,29.5,29.3,23.9,22.6,14.1.HRMS(MALDI-TOF):计算:对于C58H60N4S3:908.3974;Found:908.3945。
3,3’,5,5’-四溴-2,2’-二噻吩(10)。在5-15℃下,在1.5小时内向冰醋酸(35mnL)和氯仿(70mL)的混合溶剂中的2,2’-二噻吩(8.3g,50mmol)中逐滴添加溴(32.0g,200mmol)。接着室温搅拌溶液混合物5小时,然后回流24小时。在冷却至室温后,通过添加80mL的10%KOH水溶液猝灭反应。用CHCl3萃取混合物(2×100mL)。用水洗涤合并的萃取物,通过无水MgSO4干燥,过滤然后通过蒸发除去溶剂。从乙醇重结晶残余固体,得到浅白色晶体的期望产物(18.8g,78%)。1H NMR(400MHz,CDCl3,δ)7.06(s,2H).13C NMR(100MHz,CDCl3,δ)132.9,129.5,114.8,112.1MS(FAB):m/z481.0(M+)。
3,3’-二溴-2,2’-二噻吩(11)。在0.5小时内,将3,3’,5,5’-四溴-2,2’-二噻吩10(15g,31.1mmol)部分添加到含有15mL水的150mL的乙醇、72mL的冰醋酸以及3.1mL的3M HCl中的锌粉末(7.8g,0.12mol)的回流分散液。在回流另外2小时然后冷却至室温后,过滤混合物并用乙醇洗涤三次,收集滤液。通过蒸发去除溶剂,并添加60mL的H2O。用二氯甲烷萃取混合物(3×100mL),用水洗涤合并的萃取液,通过无水MgSO4干燥然后过滤。通过蒸发除去溶剂,从己烷结晶粗产物以得到无色的晶体产物9.2g,92%收率。1H NMR(400MHz,CDCl3,δ)7.43(d,J=5.4Hz,2H),7.09(d,J=5.4Hz,2H).13C NMR(100MHz,CDCl3,δ)130.8,128.8,127.5,112.6.MS(FAB):m/z324.0(M+)。
3,3’-双[9,9-双(正癸基)-2-二苯基氨基-7-芴基]-2,2’-二噻吩(12a)。向100双颈圆底烧瓶中添加R1-B(OH)2(790mg,1.2mmol)、11(162mg,0.5mmol)、Pd(PPh3)4(50mg)、THF(30mL)以及2M K2CO3(2.4mL)。在N2下,将溶液混合物加热至80℃过夜。在冷却至室温后,将反应混合物倾倒水中并用二氯甲烷萃取(3×30mL)。通过无水Na2SO4干燥合并的有机相,并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了无色的油状液体的期望产物(583mg,84%)。1H NMR(400MHz,CDCl3,δ)7.53(d,J=8.4Hz,2H),7.49(d,J=8.0Hz,2H),7.39(d,J=5.2Hz,2H),7.28-7.23(m,10H),7.19-7.08(m,14H),7.04-6.99(m,6H),1.74-1.62(m,8H),1.29-1.01(m,56H),0.90(t,J=7.0Hz,12H),0.57-0.55(m,8H).13CNMR(100MHz,CDCl3,δ)152.3,150.5,147.9,146.9,142.2,139.6,136.1,133.8,129.6,129.1,128.9,127.0,125.9,123.7,123.5,122.7,122.4,120.3,119.4,118.8,54.8,40.3,31.9,30.1,29.7,29.6,29.4,29.3,23.8,22.7,14.1.MS(MALDI-TOF):m/z1389.1621(M+)。
4,4’-双[9,9-双(正癸基)-2-二苯基氨基-7-芴基]-2,2’-二(2,2’:5’,2’’)-四噻吩-5’’-甲醛)-5,5’-二噻吩(14a)。向100双颈圆底烧瓶中添加由12a(486mg,0.35mmol)、1.6M n-BuLi(0.9mL,1.4mmol)和硼酸三甲酯(0.2mL,2mmol)使用典型过程制备的4,4’-双[9,9-双(正癸基)-2-二苯基氨基-7-芴基]-5,5’-二噻吩-2,2’-二硼酸13a(372mg,0.25mmol)、5-碘-2,2’:5’,2”-四噻吩-5”-甲醛(242mg,0.6mmol)、Pd(PPh3)4(25mg)、THF(20mL)以及2M K2CO3(0.5mL)。在N2下,将溶液混合物加热至80℃过夜。在冷却至室温后,将反应混合物倾倒水中并用二氯甲烷萃取(3×30mL)。通过无水Na2SO4干燥合并的有机相,并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了红色固体的期望产物(390mg,80%)。1H NMR(400MHz,CDCl3,δ)9.87(s,2H),7.69(d,J=8.0Hz,2H),7.55-7.51(m,4H),7.29-7.19(m,18H),7.13-7.07(m,16H),7.03-6.99(m,6H),1.76-1.66(m,8H),1.24-0.97(m,56H),0.85(t,J=7.0Hz,12H),0.63-0.57(m,8H).13C NMR(100MHz,CDCl3,δ)182.4,152.3,150.7,147.9,147.1,146.6,143.5,141.6,140.2,138.7,137.4,137.0,136.6,135.8,135.4,134.6,133.2,129.1,128.3,127.0,126.9,125.6,125.1,124.7,124.6,124.0,123.8,123.4,122.9,122.4,120.4,119.3,119.0,54.8,40.2,31.9,30.1,29.8,29.7,29.5,29.4,23.9,22.7,14.1.MS(MALDI-TOF):m/z1937.8069(M+)。
ADDA-1。在室温下向含有14a(300mg,0.15mmol)和氯仿(20mL)的100mL圆顶烧瓶中添加丙二睛(0.40g,6.1mmol)和吡啶(0.8mL)。在N2下,搅拌溶液混合物并加热至回流过夜。在冷却至室温后,将反应混合物倾倒入水中,用0.1M HCl中和并用CHCl3萃取(3×30mL)。用水洗涤合并的有机相,通过无水Na2SO4干燥,过滤并蒸发至干燥。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化残余固体,得到黑红色固体,该固体通过用CHCl3/CH3OH沉淀,用CH3OH洗涤然后真空干燥来进一步纯化,得到了黑色固体的期望产物(284mg,93%)。1H NMR(400MHz,CDCl3,δ)7.67(s,2H),7.55(d,J=4.4Hz,2H),7.45-7.41(m,4H),7.27(d,J=3.6Hz,2H),7.20-7.09(m,14H),7.06-6.98(m,16H),6.93-6.89(m,6H),1.66-1.54(m,8H),1.14-0.86(m,56H),0.75(t,J=7.0Hz,12H),0.51-0.49(m,8H).13C NMR(100MHz,CDCl3,δ)152.3,150.7,149.9,148.8,147.9,147.2,143.6,140.2,140.14,140.11,137.2,136.9,135.7,135.1,133.6,133.4,133.1,129.1,128.5,128.1,127.1,125.8,125.6,124.9,124.8,124.3,123.8,123.4,122.9,122.5,120.4,119.3,119.1,114.3,113.5,76.0,54.9,40.2,31.9,30.1,29.8,29.7,29.5,29.4,23.9,22.7,14.1.HRMS(MALDI-TOF):计算:对于C130H132N6S8:2033.8316;Found:2033.8320。
3,3’-双{2-二苯基氨基-7,7’-二[9,9-双(正丁基)芴]-2”-基}-2,2’-二噻吩(12b)。使用R2-B(OH)2(940mg,1.23mmol)、11(162mg,0.5mmol)、Pd(PPh3)4(40mg)、THF(30mL)以及2M K2CO3(2.4mL)来按照12a的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到无色的油状液体的期望产物(570mg,71%)。1H NMR(400MHz,CDCl3,δ)7.72-7.56(m,16H),7.42(d,J=5.2Hz,2H),7.27-7.23(m,14H),7.15-7.13(m,10H),7.05-6.99(m,6H),2.00-1.74(m,16H),1.14-0.98(m,16H),0.74-0.56(m,40H).13C NMR(100MHz,CDCl3,δ)152.4,151.7,151.4,150.9,147.9,147.1,142.3,140.3,140.1,139.9,139.6,134.5,129.8,129.1,129.0,127.1,126.1,125.9,125.8,123.8,123.5,123.0,122.5,121.2,120.3,119.9,119.5,119.4,119.3,55.1,54.9,40.3,39.9,26.1,25.9,23.1,23.0,13.88,13.86.MS(MALDI-TOF):m/z1605.0822(M+)。
4,4’-双{2-二苯基氨基-7,7’-二[9,9-双(正丁基)芴]-2”-基}-2,2’-二(2,2’:5’,2”-四噻吩-5”-甲醛)-5,5’-二噻吩(14b)。使用由12b(500mg,0.31mmol)、1.6M n-BuLi(0.8mL,1.25mmol)以及硼酸三甲酯(0.2mL,2mmol)使用标准过程制备的13b(395mg,0.23mmol)、5-碘-2,2’:5’,2”-四噻吩-5”-甲醛(242mg,0.6mmol)、Pd(PPh3)4(25mg)、THF(20mL)以及2M K2CO3(0.5mL)来按照14a的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到红色固体的期望产物(376mg,76%)。1H NMR(400MHz,CDCl3,δ)9.88(s,18H),7.78-7.59(m,18H),7.35-7.01(m,40H),2.02-1.83(m,16H),1.13-1.02(m,16H),0.76-0.62(m,40H).13C NMR(100MHz,CDCl3,δ)182.4,152.4,151.7,151.,151.1,147.9,147.1,146.6,143.4,141.7,140.5,140.5,140.2,140.1,139.7,139.5,138.7,137.4,137.2,136.6,135.9,135.5,134.7,133.9,129.1,128.4,127.2,126.9,125.7,125.2,124.8,124.7,123.8,123.4,123.0,122.5,121.3,121.1,120.4,120.0,119.7,119.3,55.0,54.9,40.2,39.9,26.1,26.0,23.1,22.9,13.9.MS(MALDI-TOF):m/z2154.8131(M+)。
ADDA-2。使用14b(300mg,0.14mmol)、丙二睛(0.40g,6.1mmol)、吡啶(0.8mL)以及CHCl3(20mL)来按照ADDA-1的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化残余固体,得到了黑红色的固体,该固体通过用CHCl3/CH3OH沉淀,用甲醇洗涤然后真空干燥来进一步纯化,得到了黑色固体的期望产物(270mg,86%)。1H NMR(400MHz,CDCl3,δ)7.76-7.44(m,4H),7.69-7.57(m,16H),7.38(d,J=4.0Hz,2H),7.33(s,4H),7.29-7.24(m,12H),7.17-7.12(m,16H),7.06-7.01(m,6H),2.01-1.81(m,16H),1.16-0.98(m,16H),0.74-0.61(m,40H).13C NMR(100MHz,CDCl3,δ)152.3,151.7,151.4,151.1,149.9,148.8,147.9,143.5,140.5,140.2,140.2,140.1,139.7,139.4,137.1,137.0,135.8,135.2,133.9,133.7,133.5,129.1,128.5,128.2,127.2,125.9,125.8,125.6,124.9,124.8,124.4,123.8,123.4,123.0,122.5,121.3,121.1,120.4,120.0,119.7,119.3,14.3,113.5,76.0,55.0,54.9,40.2,39.9,26.1,26.0,23.1,22.9,13.9.HRMS(MALDI-TOF):计算:对于C148H132N6S8:2251.0043;Found:2251.0046。
9-癸基咔唑(15)。向咔唑(2.1g,12.5mmol)、苯(10mL)、四丁基溴化铵(0.1g,0.7mmol)以及1-溴癸烷(3.0mL,15mmol)中添加50%NaOH水溶液(15mL)。将溶液混合物加热至80℃并搅拌2小时。真空蒸发溶剂并用二氯甲烷萃取残余物(3×30mL)。通过无水Na2SO4干燥有机层并过来。去除溶剂后,通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化残余物,得到了期望产物(3.4g,90%)。1H NMR(400MHz,CDCl3,δ)8.10(d,J=7.6Hz,2H),7.48-7.38(m,4H),7.24(dd,J=14.4Hz,J=1.2Hz,2H),4.30(t,J=7.2Hz,2H),1.89-1.81(m,2H),1.39-1.23(m,14H),0.88(t,J=7.0Hz,3H).13C NMR(100MHz,CDCl3,δ)140.4,125.5,122.8,120.3,118.6,108.6,43.1,31.8,29.5,29.4,29.4,29.3,28.9,27.3,22.7,14.1.MS(MALDI-TOF):m/z307.2579(M+)。
4-溴-9-癸基咔唑(16)。在0℃下,在一部分中向二氯甲烷(90mL)中的9-癸基咔唑15(3.0g,10mmol)的溶液中添加N-溴琥珀酰胺(1.80g,10.1mmol)。将混合物升温至室温并搅拌过夜。在去除溶剂后,通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化残余物,得到了期望产物(3.35g,87%)。1H NMR(400MHz,CDCl3,δ)8.19(d,J=1.6Hz,1H),8.04(d,J=8.0Hz,1H),7.53-7.45(m,2H),7.39(d,J=8.0Hz,1H),7.24-7.20(m,2H),4.26(t,J=7.2Hz,2H),1.86-1.79(m,2H),1.30-1.22(m,2H),0.88(t,J=6.4Hz,3H).13CNMR(100MHz,CDC13,8)140.7,139.0,128.2,126.3,124.5,123.0,121.8,120.5,119.1,111.5,110.1,108.9,43.2,31.8,29.5,29.4,29.3,29.2,28.9,27.2,22.6,14.1.MS(MALDI-TOF):m/z387.0912(M+)。
9-癸基咔唑-4-硼酸[R3-B(OH)2]。通过采用标准过程,在N2下,在-78℃下向含有4-溴癸基咔唑16(3.86g,10mmol)和干THF(50mL)的干的100mL双颈圆底烧瓶中逐滴添加1.6M的正丁基锂(10mL,15mmol),同时保持良好搅拌。搅拌1小时后,在一部分中添加硼酸三甲酯(2.0mL,18mmol),然后在-78℃下搅拌混合物1小时。当混合物自然升温至-30℃时,又添加水和HCl(3M)。接着,将反应混合物倾倒入用乙酸乙酯(3×50mL)萃取的水团块中。用无水Na2SO4干燥合并的有机层,过滤并在35℃下蒸发至干燥。接着将粗产物加载到硅胶柱上并用二氯甲烷和石油醚/乙酸乙酯洗脱,得到浅白色的固体(3.6g,68%)。1H NMR(400MHz,DMSO-d6,δ)8.59(s,1H),8.10(d,J=7.6Hz,1H),7.93-7.88(m,3H),7.59-7.52(m,2H),7.45-7.41(m,1H),7.22-7.18(m,1H),4.39-4.37(m,2H),1.76-1.74(m,2H),1.25-1.16(m,14H),0.84(t,J=7.4Hz,3H).13C NMR(100MHz,DMSO-d6,δ)141.6,140.1,131.8,125.5,122.3,121.5,119.9,118.9,109.3,108.3,42.2,31.3,28.9,28.8,28.7,28.6,28.5,26.5,22.1,13.9.MS(FAB):m/z(M+)。
3,3’-双(N-癸基-3-咔唑)-2,2’-二噻吩(17)。使用硼酸[R3-B(OH)2](630mg,1.8mmol)、11(243mg,0.75mmol)、Pd(PPh3)4(50mg)、THF(30mL)以及2M K2CO3(3.6mL)来按照12a的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了无色固体的期望产物(490mg,84%)。1H NMR(400MHz,CDCl3,δ)7.74(d,J=8.0Hz,2H),7.62(d,J=1.2Hz,2H),7.40-7.39(m,4H),7.29-7.26(m,2H),7.19-7.12(m,6H),7.03(d,J=8.4Hz,2H),4.07(t,J=7.2Hz,4H),1.79-1.74(m,4H),1.33-1.27(m,28H),0.92(t,J=8.6Hz,6H).13C NMR(100MHz,CDCl3,δ)141.7,140.4,139.1,129.8,129.5,126.9,126.2,125.4,125.3,122.7,122.4,120.3,119.9,118.4,108.5,107.8,42.7,31.8,29.5,29.4,29.3,28.9,27.3,22.7,14.1.MS(MALDI-TOF):m/z776.1193(M+)。
4,4’-双(N-癸基-3-咔唑)-2,2’-二(2,2’:5’,2”-四噻吩-5”-甲醛)-2,2’-二噻吩(19)。使用由17(400mg,0.51mmol)、1.6M n-BuLi(1.2mL,2.0mmol)以及硼酸三甲酯(0.3mL,3mmol)使用标准过程制备的4,4’-双(N-癸基-3-咔唑)-5,5’-二噻吩-2,2’-二硼酸18(357mg,0.41mmol)、5-碘-2,2’:5’,2”-四噻吩-5”-甲醛(363mg,0.9mmol)、Pd(PPh3)4(40mg)、THF(20mL)以及2M K2CO3(1.0mL)来按照14a的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化粗产物,得到了红色固体的期望产物(402mg,74%)。1H NMR(400MHz,CDCl3,δ)9.87(s,2H),7.72(d,J=7.6Hz,2H),7.68(d,J=4.0Hz,2H),7.58(d,J=0.9Hz,2H),7.40-7.36(m,2H),7.29-7.22(m,8H),7.18-7.10(m,10H),7.02(d,J=8.4Hz,2H),4.03(t,J=7.2Hz,4H),1.77-1.73(m,4H),1.31-1.24(m,28H),0.88(t,J=6.8Hz,6H).13C NMR(100MHz,CDCl3,δ)182.4,146.7,142.8,141.5,140.4,139.3,138.8,137.4,136.9,136.3,135.1,134.4,128.4,126.9,126.8,126.3,126.1,125.4,125.1,124.5,124.0,122.5,120.2,119.9,118.5,108.5,107.9,42.8,31.8,29.5,29.4,29.3,28.9,27.3,22.6,14.1.MS(MALDI-TOF):m/z1324.3371(M+)。
ADDA-3。使用19(292mg,0.22mmol)、丙二睛(0.40g,6.1mmol)、吡啶(0.8mL)以及CHCl3(20mL),按照ADDA-1的合成过程。通过硅胶色谱柱使用石油醚/二氯甲烷作为洗脱剂来纯化残余固体,得到了黑红色的固体,该固体通过用CHCl3/CH3OH沉淀,用甲醇洗涤然后真空干燥来进一步纯化,得到了黑色固体的期望产物(266mg,85%)。1H NMR(400MHz,CDCl3,δ)7.73(s,2H),7.72(d,J=7.6Hz,2H),7.61(d,J=4.4Hz,2H),7.58(d,J=1.2Hz,2H),7.41-7.34(m,4H),7.25-7.22(m,6H),7.18-7.12(m,10H),7.02(d,J=8.4Hz,2H),4.03(t,J=7.2Hz,4H),1.76-1.73(m,4H),1.30-1.23(m,28H),0.88(t,J=6.8Hz,6H).13C NMR(100MHz,CDCl3,δ)149.9,148.9,142.9,140.4,140.3,140.2,139.4,137.6,136.2,134.8,133.5,133.4,128.6,128.2,127.0,126.2,126.1,125.7,125.5,124.9,124.6,124.3,122.5,122.4,120.2,119.9,118.6,114.3,113.5,108.6,108.0,75.9,42.9,31.9,29.5,29.4,29.3,28.9,27.3,22.7,14.1.HRMS(MALDI-TOF):计算:对于C84H72N6S8:1421.3619;Found:1421.3643。
下面的表1显示了基于三氰基乙烯基的低聚噻吩化合物1(PhN-OF(2)OT(n)-TCN)和2(PhN-OFFT-TCN)的物理测量结果的概述。对于化合物1,具体体现为n=2和3(PhN-OF(2)OT(2)-TCN和PhN-OF(2)OT(3)-TCN)。
表1基于三氰基乙烯基的低聚噻吩(化合物1和2)的物理测量结果的概述。
λabs max:最大吸收波长;Eoxd 1:第一氧化能量波;Ered 1:第一还及次级原能量波;HOMO:最高占据分子轨道;LUMO:最低未占据分子轨道;Tg:玻璃化转变温度;Tm:熔化温度;Tdec:分解温度。a在CHCl3中测量。b在薄膜中测量。c由薄膜的吸收边缘估计的。d通过CV法使用铂盘电极作为工作电极,铂线作为辅助电极以及SCE作为参比电极,且琼脂盐桥连接到低聚物溶液以及二茂铁用作外部标准品,E1/2(Fc/Fc+)=0.45V对SCE且由二茂铁计算(4.8eV对真空)。e能隙=HOMO-LUMO。f在N2下通过差示扫描量热计由冷却后重新熔化且加热速率为40℃/分钟来测定。g在N2下通过热重分析仪且加热速率为10℃/分钟来测定。
通过紫外-可见光在薄膜中检验了新颖的基于三氰基乙烯基低聚噻吩的物理特性,如图1所示。分别通过差示扫描量热(DSC)和热重分析(TGA)研究了这些新颖的低聚噻吩的热行为和稳定性。通过循环伏安法(CV)和差式脉冲伏安法(DPV)技术研究了这些低聚噻吩的电化学特性。所有结果概述在表1中。
如表1所示,由所体现的基于三氰基低聚噻吩化合物(化合物1和2)制备的薄膜显示出1.53eV到1.73eV范围内的光学带隙,且化合物(PhN-OF(2)OT(3)-TCN)显示了1.53eV的最低光学带隙。强的吸电子三氰基乙烯基有效地将低聚噻吩的最低未占据分子轨道(LUMO)水平降低至约3.9eV,这是用于匹配可溶液处理的本体异质结PV电池的PCBM供体材料的LUMO水平的理想的LUMO水平。
下面的表2显示了基于二氰基乙烯基的低聚噻吩化合物3(ADDA-1和ADDA-2)和4(ADDA-3)的物理测量结果的概述。对于化合物3,具体体现为ADDA-1n=1和ADDA-2n=2。
发现这些非平面的低聚噻吩在固态薄膜中显示出显著的光谱加宽和大于100nm且高达150nm吸收截止的大的红移,尤其对于ADDA-3,这归因于噻吩环的受限的旋转且固态内存在分子内相互作用,导致光学带隙缩窄至1.68eV。
表2基于二氰基乙烯基的低聚噻吩(化合物1和2)的物理测量结果的概述。
λabs max:最大吸收波长;Eoxd 1:第一氧化能量波;Ered p:第一还及次级原能量波;HOMO:最高占据分子轨道;LUMO:最低未占据分子轨道;Tg:玻璃化转变温度;Tm:熔化温度;Tdec:分解温度。a在CHCl3中测量。b在薄膜中测量。c由薄膜的吸收边缘估计的。d通过CV法使用铂盘电极作为工作电极,铂线作为辅助电极以及SCE作为参比电极,且琼脂盐桥连接到低聚物溶液以及二茂铁用作外部标准品,E1/2(Fc/Fc+)=0.47V对SCE且由二茂铁计算(4.8eV对真空)。e能隙=HOMO-LUMO。f在N2下通过差示扫描量热计由冷却后重新熔化且加热速率为40℃/分钟来测定。g在N2下通过热重分析仪且加热速率为10℃/分钟来测定。
通过紫外-可见光在薄膜中检验了新颖的基于二氰基乙烯基低聚噻吩的物理特性,如图1所示,且结果概述在表2中。如表2所示,由化合物3和4制备的薄膜显示出1.68eV到1.91eV范围内的光学带隙,且化合物4显示了1.68eV的最低光学带隙。
构建到缠结的核上的化合物3和4的具有供体-受体***的非平面的基于二氰基的低聚噻吩能够有效地防止聚集。它们的处于固态的物理特性具有极大的改进。
合成了一系列新的可溶液处理的、p型和低的光隙、双供体和双受体、非平面的低聚噻吩,在噻吩核的3位和3’位具有二苯基氨基芴基或咔唑衍生物作为供体和二氰基乙烯基封端的低聚噻吩作为受体。三种非平面的低聚噻吩显示出良好的热稳定性,在500-800下在薄膜中强的吸收以及~5.2eV的相对高的氧化电势且1.91-1.68eV范围内的低光学带隙。除了它们的源于缠结的二噻吩骨架的非平面结构外,这些新合成的低聚噻吩的物理特性提出它们有希望应用于本体异质结PV电池的可溶液处理的供体材料。
Claims (4)
1.一种使用在太阳能电池应用中的化合物,该化合物具有式I所示的结构:
其中,n选自2到3的范围。
2.一种使用在太阳能电池应用中的化合物,该化合物具有式II所示的结构:
3.一种使用在太阳能电池应用中的化合物,该化合物具有式III所示的结构:
其中,n选自1到2的范围。
4.一种使用在太阳能电池应用中的化合物,该化合物具有式IV所示的结构:
其中,n选自1到2的范围。
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