Department of Chemistry and Biochemistry and the Materials Technology Center, Southern Illinois University , Carbondale, Illinois 62901, United States.
X-ray Science Division, Argonne National Laboratory , 9700 South Cass Ave., Argonne, Illinois 60439, United States.
J Am Chem Soc. 2017 Apr 26;139(16):5801-5807. doi: 10.1021/jacs.6b12916. Epub 2017 Apr 12.
We report a nontraditional synthesis of cyclopentafused-polycyclic aromatic hydrocarbon embedded ladder polymers using a palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction. Donor-acceptor type polymers containing a cyclopenta[hi]aceanthrylene acceptor groups can be synthesized by a palladium catalyzed copolymerization between 9,10-dibromoanthracene and a variety of bis(arylethynyl)arenes to give polymers with molecular weights (Mn) of 9-22 kDa. The bis(arylethynyl)arenes were composed of benzene, thiophene, or thieno[3,2-b]thiophene moieties, which provided access to a series of four donor-acceptor copolymers. The polymers were subjected to cyclodehydrogenation with FeCl to access rigid ladder type polymers with the conversion investigated by C NMR of isotopically labeled polymers. The ladder polymers possess broad UV-Vis absorptions and narrow optical band gaps of 1.17-1.29 eV and are p-type semiconductors in organic field effect transistors.
我们报告了一种使用钯催化的环戊烷聚合反应 followed by 环脱氢反应来合成环戊并稠合多环芳烃嵌入梯形聚合物的非传统方法。通过钯催化的 9,10-二溴蒽和各种双（芳基乙炔基）芳烃之间的共聚反应，可以合成含有环戊[嗨]吖啶受体基团的给体-受体型聚合物，得到分子量（Mn）为 9-22 kDa 的聚合物。双（芳基乙炔基）芳烃由苯、噻吩或噻吩[3,2-b]噻吩部分组成，这为一系列四种给体-受体共聚物提供了途径。这些聚合物用 FeCl 进行环脱氢反应，得到刚性梯形聚合物，通过对同位素标记聚合物的 C NMR 研究转化率。梯形聚合物具有宽的紫外-可见吸收和窄的光学带隙为 1.17-1.29 eV，并且在有机场效应晶体管中是 p 型半导体。
