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

Abstract

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 (DPn = 50, 93, and 128) accompanying countercations of a perylene diimide (PDI) derivative having a cyclic ammonium salt group (IIL/III and IIC/III, respectively). The subsequent heating treatment at 180 °C produced the covalently converted product, i.e., the linear IVL and the cyclic IVC, 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) m...