π-Conjugated Donor−Acceptor Copolymers Constituted of π-Excessive and π-Deficient Arylene Units. Optical and Electrochemical Properties in Relation to CT Structure of the Polymer
π-Conjugated Donor−Acceptor Copolymers Constituted of π-Excessive and π-Deficient Arylene Units. Optical and Electrochemical Properties in Relation to CT Structure of the Polymer
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DOI：
10.1021/ja961550t
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发表时间：
1996-10
影响因子：
15
通讯作者：
Takakazu Yamamoto;Zhen-hua Zhou;T. Kanbara;M. Shimura;K. Kizu;T. Maruyama;Yoshiyuki Nakamura;T. Fu
中科院分区：
文献类型：
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作者：
Takakazu Yamamoto;Zhen-hua Zhou;T. Kanbara;M. Shimura;K. Kizu;T. Maruyama;Yoshiyuki Nakamura;T. Fu
用有机金属缩聚方法(i) n X -Ar -Ar ' - X + n Ni(0)Lm→(-Ar -Ar ')-n （X =卤素，Ni(0)Lm =零价镍配合物），（ii） n X -Ar - X + n Me3Sn -Ar ' - SnMe3→(-Ar -Ar ')-n（钯催化），（iii） a X -Ar - X + b X -Ar ' - X + (a + b)Ni(0)Lm→（-Ar） X (Ar '))-y，制备了由π-过量噻吩、硒烯或呋喃单元（Ar）和π-缺吡啶或喹啉（Ar '）单元组成的各种π共轭共聚物。粉末x射线衍射分析证实了用该方法制备的聚合物的另一种结构。共聚物的分子量为5.4 × 103 ~ 3.3 × 105， [η]值为0.37 ~ 4.4 dL g-1。与(-Ar)-n和(-Ar ')-n相对应的均聚物相比，共聚物的π−π*吸收带普遍表现出红移，红移是由共聚物的电荷转移CT结构引起的。例如，噻吩和2,3-二苯基喹啉的可选共聚物可产生吸收…
Various π-conjugated copolymers constituted of π-excessive thiophene, selenophene, or furan units (Ar) and π-deficient pyridine or quinoxaline (Ar‘) units have been prepared in high yields by the following organometallic polycondensation methods: (i) n X−Ar−Ar‘−X + n Ni(0)Lm → (-Ar−Ar‘)-n (X = halogen, Ni(0)Lm = zerovalent nickel complex), (ii) n X−Ar−X + n Me3Sn−Ar‘−SnMe3 → (-Ar−Ar‘)-n (palladium catalyzed), and (iii) a X−Ar−X + b X−Ar‘−X + (a + b)Ni(0)Lm → (-Ar)x(Ar‘)-y. Powder X-ray diffraction analysis confirms an alternative structure of a polymer prepared by the method ii. The copolymers have a molecular weight of 5.4 × 103 to 3.3 × 105 and an [η] value of 0.37 to 4.4 dL g-1. π−π* absorption bands of the copolymers generally show red shifts from those of the corresponding homopolymers, (-Ar)-n and (-Ar‘)-n, and the red shifts are accounted for by charge-transferred CT structures of the copolymers. For example, an alternative copolymer of thiophene and 2,3-diphenylquinoxaline gives rise to an absorp...