REGIOCONTROLLED SYNTHESIS OF POLY(3-ALKYLTHIOPHENES) MEDIATED BY RIEKE ZINC - THEIR CHARACTERIZATION AND SOLID-STATE PROPERTIES
REGIOCONTROLLED SYNTHESIS OF POLY(3-ALKYLTHIOPHENES) MEDIATED BY RIEKE ZINC - THEIR CHARACTERIZATION AND SOLID-STATE PROPERTIES
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DOI：
10.1021/ja00106a027
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发表时间：
1995-01-11
影响因子：
15
通讯作者：
RIEKE, RD
中科院分区：
文献类型：
--
作者：
CHEN, TA;WU, XM;RIEKE, RD
报道了一种由Rieke锌介导的聚3-烷基噻吩（P3 AT）的区域控制合成方法。将Rieke锌区域选择性地氧化加成至2，5-二溴-3-烷基噻吩或2-溴-5-碘-3-烷基噻吩，得到2-溴-5-（溴锌基）-3-烷基噻吩（2）或2-溴-5-（碘锌基）-3-烷基噻吩（10）。中间体2或10可以使用不同的催化剂催化聚合成一系列区域特异性聚（3-烷基噻吩）。聚合物链的区域规整性仅由催化剂的结构控制。通过使用Ni（DPPE）Cl-2（[1，2-双-（二苯基膦基）乙烷]氯化镍（II））获得几乎完全区域规则的头-尾（HT）P3 AT（4）。使用Pd（DPPE）Cl-2导致区域规则性（70：30 HT/HH）降低，而使用Ni（PPh（3））（4）也导致区域规则性P3 AT（63：35 HT/HH）大大降低。用Pd（PPh（3））（4）得到完全区域无规的（50：50 HT/HH）P_3AT（5）。聚（3-丁基噻吩）4a是97%HT区域规整聚合物。其它聚（3-烷基噻吩）（烷基=己基（4 b）、辛基（4c）、癸基（4d）、十二烷基（4 e）和十四烷基（4f））是基于NMR分析的HT键大于98.5%的区域规则P3 AT。电子吸收、X射线衍射和正交偏光显微镜研究表明，区域规则P3 ATs（4）的铸膜是自组织的、结晶的、柔性的、具有金属光泽的青铜色膜，而区域无规P3 ATs（5）的铸膜是无定形的、橙色膜。区域规则的P3 AT表现出小的带隙（1.7 eV），其比区域无规的P3 AT的带隙（2.1 eV）低0.4 eV。与区域无规P3 AT相比，区域有规HT P3 AT具有显著改善的电导率和其他物理性质。
A systematically regiocontrolled synthesis of poly(3-alkylthiophenes) (P3AT) mediated by Rieke zinc is reported. Rieke zinc undergoes oxidative addition to 2,5-dibromo-3-alkylthiophene or 2-bromo-5-iodo-3-alkylthiophene regioselectively to afford 2-bromo-5-(bromozincio)-3-alkylthiophene (2) or 2-bromo-5-(iodozincio)-3-alkylthiophene (10). The intermediate 2 or 10 can be polymerized catalytically to a series of regiospecific poly(3-alkylthiophenes) using different catalysts. The regioregularity of the polymer chain is solely controlled by the structure of the catalyst. An almost completely regioregular head-to-tail (HT) P3AT (4) is obtained by using Ni(DPPE)Cl-2 ([1,2-bis-(diphenylphosphino)ethane]nickel(II) chloride). Use of Pd(DPPE)Cl-2 leads to a reduction in the regioregularity (70:30 HT/HH), while using Ni(PPh(3))(4) also leads to a much reduced regioregular P3AT (63:35 HT/HH). A totally regiorandom (50:50 HT/HH) P3AT (5) is afforded by using Pd(PPh(3))(4). The poly(3-butylthiophene) 4a is a 97% HT regioregular polymer. Other poly(3-alkylthiophenes) (alkyl = hexyl (4b), octyl (4c), decyl (4d), dodecyl (4e), and tetradecyl (4f)) are regioregular P3ATs with the HT linkage larger than 98.5% based on NMR analysis. Electronic absorption, X-ray diffraction, and crossed polarizing micrograph studies show that the cast films of the regioregular P3ATs (4) are self-organized, crystalline, flexible, and bronze-colored films with a metallic luster, while that of the regiorandom P3ATs (5) are amorphous and orange-colored films. The regioregular P3ATs exhibit a small bandgap (1.7 eV) which is 0.4 eV lower than that of regiorandom P3ATs (2.1 eV). Regioregular HT P3ATs have considerably improved electroconductivity and other physical properties over regiorandom P3ATs.