ESA-CF Synthesis of Linear and Cyclic Polymers Having Densely Appended Perylene Units and Topology Effects on Their Thin-Film Electron Mobility

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• 作者：Akihiro Kimura ; Tsukasa Hasegawa ; Takuya Yamamoto ; Hidetoshi Matsumoto ; Yasuyuki Tezuka
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：August 23, 2016
• 年：2016
• 卷：49
• 期：16
• 页码：5831-5840
• 全文大小：602K
• 年卷期：0
• ISSN：1520-5835

文摘

A pair of topologically contrastive, linear and cyclic polymers having densely appended perylene diimide (PDI) units have been prepared by means of an electrostatic self-assembly and covalent fixation (ESA-CF) process, using an assembly composed of either linear or cyclic polyacrylate anions of different segment lengths (DP_n = 50, 93, and 128) accompanying countercations of a perylene diimide (PDI) derivative having a cyclic ammonium salt group (II_L/III and II_C/III, respectively). The subsequent heating treatment at 180 °C produced the covalently converted product, i.e., the linear IV_L and the cyclic IV_C, respectively, in which the PDI unit was introduced nearly quantitatively to the backbone acrylate units. The obtained linear and cyclic polymers having pendant PDI units were observed to form commonly spherical self-assemblies both in bulk and in solution states, while the solution viscosity was noticeably higher with the linear products than with the cyclic counterparts. The electron-only device (EOD) measurement by using thin-film samples of a series of cyclized products, IV_C, revealed consistently higher electron carrier mobilities in comparison with the corresponding linear counterparts, IV_L.