CN102292374A - 具有高电荷载流子迁移性的黑色可溶性共轭聚合物 - Google Patents
具有高电荷载流子迁移性的黑色可溶性共轭聚合物 Download PDFInfo
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- CN102292374A CN102292374A CN2009801552406A CN200980155240A CN102292374A CN 102292374 A CN102292374 A CN 102292374A CN 2009801552406 A CN2009801552406 A CN 2009801552406A CN 200980155240 A CN200980155240 A CN 200980155240A CN 102292374 A CN102292374 A CN 102292374A
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- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
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Abstract
制备了一种可溶性稠合给体-受体共轭聚合物(fDA-CP),其接近在全部可见光谱上吸收光,当其为中性态时对人眼显示为基本上黑色。共轭聚合物具有通过多个稠合给体单元分开的受体单元。fDA-CP设计了一种结构,得到了紧密的相邻层之间的π-叠合,其具有低于
Description
相关申请的交叉引用
本申请要求序号为61/118,316的于2008年11月26日提交的美国临时申请的优先权,将其全部内容(包括任意图、表或附图)引入本文作为参考。
发明背景
包括富电子和弱π共轭取代基的分子系统已经合成来用于能带混合(energy band mixing)应用场合。这些分子系统已经被探索用作:发光半导体;用于有机薄膜晶体管的n-通道和双极性半导体;用于化学生物传感器的活性有机组件;非-发射性有机电致发色;和在电磁波谱可见光和/或近红外线(NIR)区域进行吸收的低-带隙光电部件。为了设计具有高能量转化率的本体-异质结(bulk-heterojunction)太阳能电池,已经发展在可见光和/或近红外(NIR)区域进行吸收的低-带隙光电部件。可以通过结构控制来容易地进行带隙设计(bandgap engineer)并且允许机械形变的给体-受体(DA)π-共轭聚合物,对高性能柔性光采集新技术而言,是值得注意的。与无机对应物相反,DA π-共轭聚合物具有可低成本放量和高生产率溶液加工的潜力,特别对于需要大面积的太阳能电池最终应用场合而言,例如,在汽车和建筑外表面,或者需要如在便携式电子设备中的精细印刷的光活性阵列。
虽然该给体-受体型高分子已经在超过十年前就由Havinga等人,Synthetic Metals,1993,55,(1),299-306进行了介绍,仅仅最近,才有共轭聚合物被合成,其显示了用于光伏电池的良好性能(多达5%的总效率)。一般地,DA聚合物已经显示了低功率转换效率。该低效率归因于两个原因。第一原因是,DA聚合物的光吸收一般限于可见光谱的一小部分,一般是红色区域。另一个原因是,DA聚合物在固体状态设备中,显示低的固有电荷载流子迁移率。
很少有公开实现了大区段可见光谱的吸收、因此是基本为黑色的体系。几乎所有的设计用于全频带可见光吸收的聚合物都依赖于仅仅少量的宽吸收发色团或具有多个均匀分布在可见光谱上的窄吸收特征的发色团。仅仅在最近才报道了,第一个太阳能电池系统,其包括了具有在整个可见光谱上的吸收的全有机聚合物半导体,甚至这些系统也没有在整个可见区都具有强烈的吸收(>50%的峰值吸收),(参见Hou等人的J.Amer.Chem.Soc.,11/07/2008互联网公开,其说明了交替共聚物poly[(4,4’-bis(2-ethylhexyl)dithieno[3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(2,l,3-benzothiadiazole)-4,7-diyl](PSBTBT),和Wang等人的Appl.Phys.Lett.2008,92,033307,其说明了交替共聚物poly[(2,7-dioctylsilafluorene)-2,7-diyl-α/t-(4,7-bis(2-thienyl)-2,l,3-benzothiadiazole)-5,5’-diyl](PSiFDTBT))
由于缺少良好的分子间相互作用,具体地说,弱π-叠合性(其原因是由于链段与链段之间的长距离,也被称为层间距,以及因为聚合物主链的低水平的平面性而缺乏扩展的共轭性),典型的强吸收的DA聚合物显示出有限的电荷载流子迁移性。本体-异质结太阳电池需要高的电荷载流子迁移性,因为光产生的激子或成对的电子空穴对必须在设备的活动层内部进行扩散和离解过程,并且离解的电荷要快速输送到收集电极上。当没有高的电荷载流子迁移性时,该离解的电荷在被收集前发生复合,导致了显示弱太阳能转换率的设备。
因此在整个可见光谱上都具有强烈吸收并且对于高的电荷载流子迁移性显示出良好的π-叠合和扩展的共轭性的基本上黑色的DA聚合物系统,对于大面积柔性光采集设备,诸如太阳能电池,仍旧是发展目标。
发明概述
本发明的实施方案涉及可溶性稠合给体-受体共轭聚合物(fDA-CP),其具有为贫电子芳族结构部分的孤立的受体单元,其靠近含有增溶性侧链的多个稠合给体单元并通过含有增溶性侧链的多个稠合给体单元分开。fDA-CP在整个可见光谱上吸收光,对人眼显示为黑色。因为它们的结构,发生了相邻的聚合物链的π-叠合,其具有低于的固态层间(interlamella)分离,并可接近于以间隔的石墨的石墨烯(graphene)平面的。在本发明的许多实施方案中,稠合的给体单元以受体重复单元之间的偶数的单分散的序列存在。在一些实施方案中,该稠合给体单元可具有如下结构:
其中E是-CH=CH-,S,Se,NH,NR,或者Si;X是C,Si,或者N;m是1到5;p是0或者1;并且R是直链或支化C1-24烷基,直链或支化的C2-24烯基,或者用H,甲基,C2-6烷基,或芳基取代的直链或支化的Si1-10硅烷或硅氧烷,或者其它增溶基团。受体单元可以是噻二唑喹喔啉(thiadiazoloq uinoxaline),喹喔啉,噻吩并噻二唑(thienothiadiazol),噻吩并吡嗪(thienopyrazine),吡嗪并喹喔啉(pyrazinoquinoxaline),苯并噻二唑(benzothiadiazole),双-苯并噻二唑,或者噻二唑噻吩并吡嗪(thiadiazolothienopyrazine)的衍生物。在一些实施方案中,该受体单元是2,1,3-苯并噻二唑。在其它实施方案中,附加的共轭芳族单元,例如未被取代的噻吩单元,可以居于稠合给体单元之间。根据本发明的实施方案,fDA-CP的示例性结构包括:
其中,A是包括贫电子芳族结构部分的受体单元;E是-CH=CH-,S,Se,NH,NR,或者Si;X是C,Si,或者N;n是5到100;m是1到5;x是1到5;p是0或者1;并且R是直链或支化的C1-24烷基,直链或支化的C2-24烯基,或者用H,甲基,C2-6烷基,或芳基取代的直链或支化的Si1-10硅烷或硅氧烷,或者其它增溶基团。
本发明的其它实施方案涉及fDA-CP的制备方法,其具有fDA-低聚物的聚合反应混合物,所述fDA-低聚物具有一个或者多个具有贫电子芳族结构部分的受体单元,所述芳族结构部分通过稠合给体单元分开,其中给体单元居于fDA-低聚物的各端,并且进行被化学聚合来生成上述类型(1)或(2)的fDA-CP。聚合反应混合物还可含有具有至少一个共轭芳族单元的共轭单体或低聚物,其中通过聚合来形成上述类型(3)的fDA-CP。
附图说明
图1显示了根据本发明实施方案的稠合的给体和受体的构型,其导致了具有高电荷载流子迁移性的黑色可溶性共轭聚合物。
图2显示了根据本发明实施方案的fDA-低聚物,其可用于制备根据本发明实施方案的fDA-CP。
图3显示了根据本发明的实施方案的一些可居于fDA-CP的fD单元之间的共轭单元的实例,其为单体或者2到5的低聚物单元。
图4显示了根据本发明实施方案的fDA-CP的两个取代的受体单元的实例。
图5显示了根据本发明实施方案的用于制备fDA-CP的示例性方法。
图6显示了根据本发明实施方案的用于制备在fD单元之间具有非-噻吩共轭重复单元的fDA-CP的示例性方法。
图7显示了根据本发明实施方案的三个fDA-CP的可见光吸收谱的综合,其显示了在几乎全部可见光谱上的超过50%的峰值吸收的吸收率。
发明详述
近来,本发明人已经发展出了一类给体-受体电致发色聚合物(DA-ECP),其在可见光中显示出吸收,其中通过变化聚合物重复单元中富电子和贫电子结构的相对贡献来控制多重能量转换,从而实现了第一种黑色聚合物电致发色材料。该DA-ECP具有重叠的短波长和长波长谱带,并产生了拥有各种色调和饱和度的中性态着色材料,其中至少两个给体单元使受体单元分开,来产生具有扩展到整个可见光谱的吸收光谱的共聚物,并得到中性状态黑色聚合物。因为增溶性侧链的存在,该DA-ECP使用适当的沉积方法,可很容易地加工成电致发色装置,诸如通过旋涂,喷雾-流延,和各种印刷方法(例如喷墨打印)。中性聚合物载整个可见光谱区上的吸收,及其电荷迁移性能一起,允许该新型给体-受体共轭聚合物(DA-CP)用于黑色太阳能电池。
该黑色中性状态DA-CP具有含有孤立的内部受体单元,或者孤立序列的受体单元的结构,其通过两个或多个给体单元的序列来与其它受体单元分开。DA-CP的吸收光谱依赖于给体和受体单元的比例。一般地,DA-CP的低能最大吸收和高能最大吸收之间的波长差变得更小,同时保持了吸收峰或者增加了它们的宽度,并在波长最大值的差值降低的同时,实现了更大的重叠。这些聚合物公开在Beaujuge等人,国际申请No.PCT/US2008/081606,2008年10月29日提交,在此引入作为参考。Beaujuge等人,Nature Materials,2008,7,795-9说明了黑色DA-CP的性能,在此引入作为参考。
本发明人已经发现,通过选择DA-CP的给体重复单元,其是具有平面内和平面外增溶性侧链的稠合平面芳族结构,π-共轭聚合物可形成,其在中性状态下是有效的黑色,并显示了对固态下的有序化(order)和/或π-叠合的高度倾向。通过明智选择这些稠合平面给体(fD),并相对于贫电子芳族受体重复单元进行合理放置,该稠合给体-受体共轭聚合物(fDA-CP)获得具有长的平面共轭序列的构象,其方式使得相邻的聚合物链的π-叠合很容易发生,其层间距接近在石墨中观察到的石墨烯层间距根据本发明实施方案的一些fDA-CP在图1中有所描述,并可用于太阳能电池应用场合。
根据本发明的实施方案,聚合物的重复序列包含一受体单元,其在侧面具有至少一个fD单元,使得每个非末端受体均与其它受体通过至少两个fD单元分开,如图1的第二式所示。正如Beaujuge等人公开的DA聚合物,在整个可见光区上具有强烈吸收的中性状态聚合物所需要的特性已由在此公开的fDA-CP来实现,而且fD的使用,而不是Beaujuge等人的示例性聚合物中的D单元的使用,允许了fDA-CP的有利的π-叠合。另外,fD单元提供了增溶性的侧基,其允许了fDA-CP在溶液状态下的增溶,并能够促进链的平面化和π-叠合。在本发明的另一个实施方案中,两个fD单元或者两个fD单元序列可通过一个或者多个共轭重复单元的序列来分开,所述共轭重复单元如图1的第一式所示。在本发明的一个实施方案中,共轭重复单元的全部序列是单分散的,并且可以是1到5个重复单元长度。在本发明的实施方案中,在A单元各侧的序列中的fD单元可以是1到5个重复单元长度。在本发明实施方案中,fD单元序列可以是单分散的。
图2说明了,可聚合或者共聚合形成根据本发明实施方案的fDA-CP的低聚物。fD单元可以是具有两个芳族单元的单个稠合给体,正如在(A)或(B)中,具有多个芳族单元的单个稠合给体,正如在(D)中,或者可以是多个稠合给体,正如在(C)中。fDA-低聚物单元可以是图2的任何结构,其中:m是1到5;p是0到1;E是S,NH,NR,Se,O或者-CH=CH-;X是C或Si,NH或NR;Z是H,Cl,Br,或者I;并且R是增溶性基团,其包括:直链或支化烷基链段,例如,1-24碳原子,其是,例如,甲基,乙基,正丙基,正丁基,仲丁基,叔丁基,正己基,正辛基,2-乙基己基,正壬基,正癸基,正十一基,正十二烷基,正十三烷基,正十四烷基,正十六烷基,正十八烷基或十二烷基;或者2-24碳原子的直链或支化的链烯基链段,例如,乙烯基,丙烯基,丁烯基,戊烯基,等等。该烷基或链烯基可被一个或者多个氧原子,硫原子,-SO-,-SO2-,羰基,-COO-,-CONH-,-NH-,-CON(C1-8烷基)-或-N(C1-8烷基)-等等插入一次或者多次。例如,该烷基可被一个或多个氧原子,硫原子,羰基,-COO-,-NH-或-N(C1-8烷基)-进行插入一次或者多次。连续的或中断的烷基或链烯基还可以被如下取代一次或者多次,一个或多个C3-6环烷基基团,卤素,-OR’,-COOR’,-COOM,-SO3M,-SO3H,膦酸,-CONR’R”,-NR-R”,膦酸盐,铵盐或式-L-Ar或-C(O)-L-Ar的基团,其中:M是氮阳离子或金属阳离子;R’和R”,独立于任何可能存在的其它R’或R”,是氢;基团-L-Ar,-C(O)-L-Ar,或者-C(O)-O-L-Ar;C1-24烷基,C3-24链烯基,C3-6环烷基或C1-24烷基羰基,其可以是连续的或者被如下基团插入一次或者多次,一个或者多个氧原子,硫原子,羰基,-COO-,-CONH-,-NH-,-CON(C1-8烷基)-或-N(C1-8烷基)-,其中未中断的和中断的烷基,链烯基,环烷基或烷基羰基是未被取代的或被如下基团取代一次或者多次,一个或者多个卤素,-OH,C7-12芳烷基,C2-12烷基羰基,C1-24烷氧基,C2-24烷羧基,-COOM,-CONH2,-CON(H)(C1-8烷基),-CON(C1-8烷基)2,-NH2,-N(H)(C1-8烷基),-N(C1-8烷基)2,-SO3M,苯基,被一个或者多个C1-8烷基取代一次或多次的苯基,萘基,被一个或者多个C1-8烷基取代一次或多次的萘基,铵盐,膦酸或膦酸盐或者当附着于氮原子时,R’和R”,与它们所键接到的氮原子一起,形成5-,6-或7-元环,其是连续的或者插入-O-,-NH-或-N(C1-12烷基)-的;并且L是直接键接或连续的或者插入一个或者多个氧原子的C1-12亚烷基,并且是未取代的或者被下述一个或者多个基团取代一次或者多次:-OH,卤素,C1-8烷基,C1-24烷氧基,C2-24烷基羧基,-NH2,-N(H)(C1-8烷基),-N(C1-8烷基)2或铵盐。R可以是1到10个硅原子的硅烷或硅氧烷链段,其中Si原子具有如下取代基:C1-12烷基;芳基:杂芳基;H;OR’或OC(O)R’,其中R’是烷基;芳基;或杂芳基。
fD单元可以通过其它fD单元或者任何其它共轭单元分开。例如,fD单元可以由单噻吩单元或低聚噻吩单元分开。例如,其它可使用的共轭单元包括:单亚苯基或低聚亚苯基;单咔唑或低聚咔唑;单芴或低聚芴;单吡咯或低聚吡咯;单呋喃或低聚呋喃;单tiazolothiazole单元或低聚tiazolothiazole单元;或根据本发明实施方案的它们的任何组合。根据本发明实施方案可以被使用的一些示例性的共轭单单元在图1中说明。
fD单元的增溶基团可以是可以从增溶单元转化为不溶的那些,其方式在Reynolds等人的国际申请No.PCT/US2007/061016,“The ChemicalDefunctionalization of Polymeric Alkylenedioxyheterocyclics”,2007年1月25日提交,在2007年8月2日以国际公开No.WO2007/087587A2公开中有所描述,在此全文引入作为参考。通过在fD重复单元上使用所述增溶性基团,可溶的fDA-CP能够转化为不溶的fDA-CP,来用于使用fDA-CP的设备的环境并不有利于可溶性fDA-CP的使用的应用场合,但是在化学脱官能团之前从溶液中制造装置的能力允许了想要的本发明的溶液加工特性。
如图1和2所示,YfDmAfDmY的A单元可以是2,1,3-苯并噻二唑(BTD)(具体如图2所示),噻二唑喹喔啉,喹喔啉,噻吩并噻二唑,噻吩并吡嗪,吡嗪并喹喔啉,苯并噻二唑,苯并双噻二唑,噻二唑噻吩并吡嗪,苯并三唑的衍生物和/或其它贫电子芳族受体单元。在本发明一些实施方案中,该受体单元是平面的重复单元来促进π-叠合。在本发明一些实施方案中,受体单元可以是取代的,如图4所示的取代的苯并噻二唑和苯并三唑受体。
图5举例说明了制备根据本发明的实施方案的一种fDA-CP的方法。根据本发明的实施方案,举例说明了一种fD单元的合成,所述单元具有通过引入作为四价单元的Si原子来偶合和稠合的两个噻吩单元,其中2-溴代噻吩1在5步骤中进行转化,来提供具有单个反应活性官能团6的fD单元,其随后与双官能A单元7进行结合来形成fDA-低聚物8a。图5中给出的产物对应于R=辛基。fDA-低聚物8a可以自我缩合来形成聚合物PMB-267,如图5所示,或者可以与另一共轭单体10,m=1,或者共轭单体10,m=2,进行交叉缩合,其中8a被转化为带有10的互补官能团的低聚物9来分别生成PMB-262或者PMB-262。在本发明的这些示例性实施方案中,如下表1所示,数均分子量被发现超过了15,000g/mol,同时所述材料具有相对低的分子量分布指数(PDI)。元素分析(EA)与设计出的fDA-CP结构的EA计算值强烈吻合。
表1图5的fDA-CP聚合物的凝胶渗透色谱表征和元素分析
如图6所示,根据本发明的实施方案,可与9进行交叉缩合的共轭单体是非-噻吩单体,例如2,7-双(三甲基甲锡烷基)-9,9-二甲基芴11。正如在所有情况下,进行交叉缩合,使得多个fD单元使共聚物中的每个受体A单元分开。
fDA-CP显示了覆盖整个可见光谱区的强烈吸收,如图7所示。在大约450nm处的吸收率超过600-650nm处的最大吸收率的50%,说明根据本发明实施方案的聚合物具有在整个可见光范围内采集太阳能的潜力。图8显示了PMB-256的二维大角度X射线谱(WAXS)和链到链之间距离图。该图表明,链段是π-叠合的,一个fDA-CP的平面与另一相邻fDA-CP平面距离是其与石墨的石墨烯片层之间的距离类似。因此,这些对称的新型fDA-CP,其在各受体单元之间具有至少两个给体单元,看来具有几乎最佳的π-叠合,其同时要求聚合物的长段居于能够给出扩展平面区段的构象中,其中给出的fDA-CP的π-轨道具有广泛的重叠。在本发明的一个实施方案中,固体状态层间距低于在本发明的另一个实施方案中,固体状态层间距低于在本发明的另一个实施方案中,固体状态层间距低于约在本发明的另一个实施方案中,固体状态层间距低于约
该fDA-CP可用于聚合物太阳能电池应用场合;光生伏打器件;光检测器和光敏元件,抗静电导体,透明导体,场效应晶体管,超级电容器,电池和其它电子元件中。由于相比于其它聚合物体系其光的吸收包括了更大比例的可见光谱和更高的电荷载流子迁移性,因此本发明的各实施方案中的fDA-CP有可能具有优异的光采集效率。
材料和方法
3,3’-二-(2-乙基己基)亚甲硅基-2,2’-双噻吩5的制备
往冷却到-78℃、在己烷中的2.5M正丁基锂(22.2mL,55.6mmol)的二乙醚溶液(300mL)中,加入在100mLTHF中的3,3’-二溴代-2,2-双噻吩4(8.2g,25.3mmol)。将混合物在该温度下搅拌3小时,然后加入在THF(100mL)中的二氯代双(2-乙基己基)硅烷(9.05g,27.8mmol)。将混合物放置过夜,允许其缓慢升温到室温。然后将反应混合物倒入300mL水中,用己烷(3×150mL)进行萃取,用MgSO4干燥,并蒸发。剩余物首先用硅胶色谱(己烷)进行提纯,然后通过Kugelrohr蒸馏(BP~175℃,0.05torr)来进一步提纯,得到3.2g淡黄色液体(30%)。1H NMR(500MHz,CDCl3)δ7.19(d,J=5.5Hz,2H),7.04(d,J=5.5Hz,2H),1.41(m,2H),1.20(m,16H),0.94(t,J=6.0Hz,4H),0.82(t,J=7.0Hz,6H),0.76(t,J=7.0Hz,6H)。13C NMR(125MHz,CDCl3)δ149.2,142.8,130.1,125.2,36.2,35.9,29.2,29.1,23.2,18.0,14.5,11.1。元素分析计算值,对C24H38S2Si:C 68.83,H 9.15。测试值C 68.50,H 9.40。HRMS(APCI)计算值[M-H+]419.2257,测试值419.2275。
5-三甲基甲锡烷基-3,3’-二-(2-乙基己基)亚甲硅基-2,2’-双噻吩6的制备
将3,3’-二-(2-乙基己基)-2,2”-双噻吩5(1.96g,4.68mmol)溶解到干燥THF(120mL)中,并冷却到-78℃。将2.5M的正丁基锂的己烷溶液(1.95mL,4.91mmol)在30分钟内加入,并在-78℃下搅拌混合物3小时。允许溶液升温到0℃,然后冷却到-78℃。随后以固体形式加入三甲基锡氯化物(1.21g,6.08mmol),允许混合物升温到室温,并搅拌16小时。然后蒸发溶剂,得到黄褐色残余物,其用约20mL己烷收集,并用硅胶短塞子(使用之前,硅胶已用纯三乙胺进行处理,用己烷进行彻底洗涤)进行过滤,然后塞子用另外约100mL己烷进行洗涤。然后蒸发掉溶剂,得到2.45g(90%)的浅黄色油,其不进一步表征或者提纯即使用。
8a的制备
往250mL烧瓶中加入5-三甲基甲锡烷基-3,3’-二-(2-乙基己基)亚甲硅基-2,2’-双噻吩6(1.70g,2.92mmol),4,7-二溴代苯并[c][1,2,5]-噻二唑7(0.43g,1.46mmol),Pd2dba3(26mg,0.029mmol),和P(o-tol)3(35mg,0.117mmol)。用氩气抽空并回灌4次,然后加入甲苯(150mL)。将混合物加入到80℃,过夜。然后通过旋转蒸发来除去甲苯,通过硅胶色谱(己烷)来提纯生成的剩余物,得到1.09g(78%)的紫色黏稠油。1H NMR(500MHz):δ8.13(t,J=5.0Hz,2H)*7.85(s,2H),7.26(d,J=5.0Hz,2H),7.09(d,J=5.0Hz,2H)1.48(m,4H),1.20(m,32H),1.05(m,8H),0.85(m,24H)。13CNMR(125MHz):δ152.7,150.5,149.1,144.2,143.5,140.3,130.5,130.2,126.1,126.0,125.1,元素分析:C54H76N2S5Si2计算值C 66.89,N 2.89,H7.90;测试值C 66.86,N 2.82,H 8.17。HRMS(ESl)计算值[M-H+]969.4223,测试值969.4229。
*不是真实的三重峰,不同的峰由带有2-乙基己基基团的DTS的三个不同的可能非对映异构体(R,R),(R,S),(S,S)所导致。因为用于生成DTS起始材料的外消旋混合物,对应的非对映异构体的1∶2∶1比例导致了在8.13的峰的1∶2∶1的比例。
9的制备
往冷却到0℃的8a(1.63g,1.68mmol)在CHCl3(75mL)的溶液中,在40分钟内加入NBS(0.598g,3.36mmol)在MeCN(50mL)中的溶液。在0℃下搅拌另外1小时,然后倒入水(100mL)中,用CHCl3(3×150mL)进行萃取,在MgSO4上进行干燥,并蒸发。剩余物用硅胶色谱(己烷)进行提纯,得到1.68g(89%)的黏稠紫色油。1H NMR(500MHz):δ8.10(t,J=5.0Hz,2H)*7.83(s,2H),7.04(t,J=1.5Hz,2H),1.48(m,4H),1.20(m,32H),1.05(m,8H),0.85(m,24H).13C NMR(125MHz):δ152.5,149.6,149.3,143.0,142.9,140.5,132.6,130.2,125.7,125.0,111.9,35.9,35.7,35.7,28.9,23.2,23.0,14.1,10.8。
*不是真实的三重峰,不同的峰由带有2-乙基己基基团的DTS的三个不同的可能非对映异构体(R,R),(R,S),(S,S)所导致。因为用于生成DTS起始材料的外消旋混合物,对应的非对映异构体的1∶2∶1比例导致了在8.10的峰的1∶2∶1的比例。
PMB-267的制备和分离
将化合物8a(415mg,0.428mmol)溶解到氯仿(50mL)中。将无水FeCl3(347mg,2.14mmol,5eq)在硝基甲烷中的溶液在室温下在30分钟内逐滴加入搅拌的单体中(随着氧化剂的加入,暗紫色单体溶液逐渐转变为暗蓝绿色)。将混合物在室温下搅拌过夜。然后在甲醇(200mL)中沉淀。过滤出沉淀物,在氯仿(200mL)中再次溶解,和一水合肼(hydrazinemonohydrate)(6mL)一起搅拌3小时。在蒸发后,将浓缩物(暗蓝绿色)在甲醇(200mL)中沉淀,将沉淀物通过索格利特套筒进行过滤,用甲醇通过索格利特装置提取24小时。用氯仿萃取聚合物,通过蒸发进行浓缩,将聚合物在甲醇(200mL)中沉淀,并收集为暗色固体(170mg,41%)。1H NMR(300MHz,CDCl3)δ=8.14(bs,2H),7.87(bs,2H),7.00(br,2H),1.50-0.80(br,68H)。GPC分析:Mn=17700g/mol,Mw=59200g/mol,PDI=3.35。对于C54H74N2S5Si2,分析的计算值为:C 67.02,H 7.71,N 2.89测试值:C 66.61,H 7.52,N 2.91。
PMB-267的改进制备和分离
将化合物8a(519mg,0.535mmol)溶解到40mL CHCl3中,并将干燥空气吹泡到溶液中。然后在2小时内,在持续吹泡下,缓慢地逐滴加入无水FeCl3(434mg,2.67mmol)在2mL硝基甲烷的溶液。该混合物用空气吹泡并且搅拌9小时,然后将混合物倒入甲醇(200mL)并搅拌过夜。然后过滤沉淀物,用甲醇清洗,将固体悬浮在250mL氯仿中,并加入~5mL的一水合肼。在室温下搅拌1.5小时,然后蒸发溶剂至大约20mL体积。然后在甲醇中沉淀,过滤到纤维素套筒上,通过索格利特装置提取用甲醇(1天),己烷(1天),氯仿(1天)和氯苯(直到透明)进行提纯。氯仿和氯苯馏分然后用甲醇沉淀,在真空下干燥,分别得到290mg(56%)和50mg(10%)的暗色固体产物。氯仿馏分的GPC(THF)Mn=29,770,Mw=75,300,PDI=2.53。
PMB-262的制备
将2,5-二溴代噻吩(0.101g,0.421mmol)溶解在干燥的THF(10mL)中,并冷却到-78℃。将正丁基锂的己烷溶液(0.405mL,1.011mmol)在10分钟内加入,然后在-78℃下,搅拌混合物达1小时。随后加入三甲基锡氯化物的己烷溶液(1.09mL,1.09mmol),允许混合物升温到室温,并搅拌1小时。蒸发掉溶剂,得到10,其中m=1,为浅黄色残余物,其不进一步提纯即用于下一步骤(约98%)。将化合物9(0.475g,0.421mmol),Pd2(dba)3(2mol%)和P(o-tol)3(8mol%)加入到剩余物中,并在12mL干燥甲苯和1mL脱气无水DMF中溶解。混合物在90℃下搅拌过夜。然后在甲醇(200mL)中沉淀。将沉淀物通过索格利特套筒进行过滤,用甲醇通过索格利特装置提取24小时。用氯仿萃取聚合物PMB-262,通过蒸发进行浓缩,并且用强络合配体(二乙基二硫代氨基甲酸二乙基铵)进行处理,以便除去催化剂的任何残余痕迹,然后在甲醇(200mL)中沉淀,并收集到暗色固体(180mg,41%)。1H NMR(300MHz,CDCl3)δ=8.12(bs,2H),7.84(bs,2H),7.00(br,4H),1.50-0.80(m,68H)。GPC分析:Mn=15 900g/mol,Mw=60 100g/mol,PDI=3.8.对于C58H76N2S6Si2,计算值:C 66.36,H 7.30,N 2.67测试值:C 66.81,H 7.45,N 2.51。
PMB-256的制备
将5,5’-二溴代-2,2’-二噻吩(0.141g,0.434mmol)溶解在干燥的THF(10mL)中,并冷却到-78℃。将正丁基锂的己烷溶液(0.416mL,1.04mmol)在10分钟内加入,然后在-78℃下,搅拌混合物达2小时。随后加入三甲基锡氯化物的己烷溶液(1.13mL,1.13mmol),允许混合物升温到室温,并搅拌2小时。蒸发掉溶剂,得到10,其中m=2,为橘黄色残余物,其不进一步提纯即用于下一步骤(约98%)。将化合物9(0.489g,0.434mmol),Pd2(dba)3(2mol%)和P(o-tol)3(8mol%)加入到剩余物中,并在12mL干燥甲苯和1mL脱气无水DMF中溶解。混合物在90℃下搅拌过夜。然后在甲醇(200mL)中沉淀。将沉淀物通过索格利特套筒进行过滤,用甲醇通过索格利特装置提取24小时。用氯仿萃取聚合物,通过蒸发进行浓缩,并且用强络合配体(二乙基二硫代氨基甲酸二乙基铵)进行处理,以便除去催化剂的任何残余痕迹,然后在甲醇(200mL)中沉淀,并收集到暗色固体(250mg,51%)。1H NMR(300MHz,CDCl3)δ=8.13(bs,2H),7.85(bs,2H),7.00(br,4H),1.50-0.80(m,68H)。GPC分析:Mn 19800g/mol,Mw=64100g/mol,PDI=3.2。对于C62H78N2S7Si2,计算值:C 65.79,H 6.95,N 2.44测试值:C 66.13,H 7.19,N 2.47。
2,7-双(三甲基甲锡烷基)-9,9-二甲基芴11的制备
往9,9’-二甲基-2,7-二溴代芴(0.75g,2.13mmol)在THF(50mL)的溶液中,在-78℃加入2.5M正丁基锂在己烷中的溶液(3.4mL,8.5mmol),然后搅拌溶液30分钟。然后将溶液升温到0℃,搅拌30分钟。然后将溶液冷却到-78℃,随后加入三甲基锡氯化物(1.78g,8.9mmol),允许溶液升温到室温。将其搅拌过夜,随后将混合物倒入水(100mL)中,并且用Et2O(3×100mL)进行萃取。混合的有机萃取物用MgSO4干燥,过滤并蒸发。从乙腈中将剩余物重复结晶3次,得到0.45g(40%)的白色固体。1HNMR(500MHz):δ7.30(dd,J=7.5Hz,J=1Hz,2H),7.57(t,J=1Hz,2H),7.48(dd,J=7.5Hz,J=1Hz,2H),1.54(s,6H),0.36(s,18H)。13C NMR(125MHz):δ153.1,141.6,139.7,134.4,130.0,119.8,47.1,27.5,-9.1。
CA-172的制备
将化合物9和11加入50mL Schlenk管中,然后加入Pd2dba3(6.3mg,0.0069mmol),和P(o-tol)3(10mg,0.033mmol)在氯苯(17mL)的溶液。将混合物加热到130℃达5天,冷却到室温,然后在甲醇中沉淀。将沉淀物过滤到纤维素套筒上,通过索格利特装置提取用甲醇(1天),己烷(1天),氯仿进行提纯。然后加入二乙基二硫代氨基甲酸二乙基铵到氯仿馏分中,搅拌一小时,然后将馏分浓缩到~50mL,加热到接近沸腾,用0.45mm PTFE针筒过滤器过滤到300mL甲醇中。然后收集沉淀,在热的氯仿中重新溶解,重复所述过滤/再沉淀过程,并再次收集固体。将固体在高度真空下过夜,得到83mg(49%)的暗色固体。GPC(THF):Mn=21,135,Mw=31,580,PDI=1.49。
结构分析
使用装备有针孔校准和二维Siemens检测器的旋转阳极(Rigaku 18kW)X射线束,来进行纤维WAXS实验。对于Cu Kα辐射(λ=0.154nm),使用了双石墨单色器。使用自制小型挤出机,在升高的温度下通过长丝挤出来制备纤维。通过恒定速率运动,进行挤出,得到0.7mm细纤维。
装备有石墨单色化CuKαX射线束的θ-θSiemens D500 Kristalloflex,被用来研究薄膜中的结构。在2θ从1到34°的范围内记录衍射图像,其为散射矢量s的函数;s=(2sinθ)/λ,其中2θ是散射角。
这里、上文或下文涉及或引用的所有专利、专利申请、临时申请和公布的全部内容包括所有附图和表作为参考引入,以使它们并不与本说明书的清楚教导不一致。
应该理解的是,本文所述的例子和实施方案仅为示例,本领域技术人员可根据其做出各种改变或变化且该改变或变化包括在本申请的精神和范围之内。
Claims (26)
1.一种可溶性稠合给体-受体共轭聚合物(fDA-CP),其包含具有贫电子芳族结构部分的孤立的受体单元,其靠近并通过含有增溶性侧链的多个稠合给体单元分开,
其中所述fDA-CP在整个可见光谱上吸收光,对人眼显示为黑色,并且其中发生了相邻的聚合物链的π-叠合,固态层间距低于
3.权利要求1的fDA-CP,其中所述受体单元包含噻二唑喹喔啉,喹喔啉,噻吩并噻二唑,噻吩并吡嗪,吡嗪并喹喔啉,苯并噻二唑,双-苯并噻二唑,噻二唑噻吩并吡嗪,苯并三唑或者它们的组合的至少一种衍生物。
4.权利要求1的fDA-CP,其中所述受体单元是2,1,3-苯并噻二唑。
6.权利要求1的fDA-CP,其中所述fDA-CP包括:
其中,A是包括贫电子芳族结构部分的受体单元;E是-CH=CH-,S,Se,NH,NR,或者Si;X是C,Si,或者N;n是5到10,000;m是1到5;p是0或者1;并且R是直链或支化的C1-24烷基,直链或支化的C2-24烯基,或者用H,甲基,C2-6烷基,或芳基取代的直链或支化的Si1-10硅烷或硅氧烷,或者其它增溶基团。
7.权利要求1的fDA-CP,其进一步在所述稠合给体单元之间包含一个或者多个共轭芳族单元。
8.权利要求7的fDA-CP,其中所述共轭重复单元包含取代或者未取代的噻吩单元。
9.权利要求7的fDA-CP,其中共轭重复单元包含取代或者未取代的亚苯基单元,咔唑单元,芴单元,吡咯单元,呋喃单元,tiazolothiazole单元,或者它们的任何组合。
14.权利要求1的fDA-CP,其中所述稠合给体单元以受体重复单元之间的偶数的单分散的序列来存在。
16.权利要求15的方法,其中所述受体单元包含噻二唑喹喔啉,喹喔啉,噻吩并噻二唑,噻吩并吡嗪,吡嗪并喹喔啉,苯并噻二唑,双-苯并噻二唑,噻二唑噻吩并吡嗪或者它们的组合的至少一种衍生物。
17.权利要求15的方法,其中所述受体单元是2,1,3-苯并噻二唑。
20.权利要求15的方法,其中所述fDA-低聚物包括:
其中,A是包括贫电子芳族结构部分的受体单元;E是-CH=CH-,S,Se,NH,NR,或者Si;X是C,Si,或者N;m是1到5;p是0或者1;并且R是直链或支化的C1-24烷基,直链或支化的C2-24烯基,或者用H,甲基,C2-6烷基,或芳基取代的直链或支化的Si1-10硅烷或硅氧烷,或者其它增溶基团。
22.权利要求15的方法,其中所述聚合反应混合物进一步包含含有至少一个共轭芳族单元的单体或者低聚物,其中所述聚合所述聚合反应混合物的步骤使得所述共轭芳族单元通过所述fDA-低聚物的稠合给体重复单元与所述受体单元分开。
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