π-Electron-system-layered polymer: through-space conjugation and properties as a single molecular wire

Yasuhiro Morisaki; Shizue Ueno; Akinori Saeki; Atsushi Asano; Shu Seki; Yoshiki Chujo

doi:10.1002/chem.201103653

π-Electron-system-layered polymer: through-space conjugation and properties as a single molecular wire

Chemistry. 2012 Apr 2;18(14):4216-24. doi: 10.1002/chem.201103653. Epub 2012 Feb 28.

Authors

Yasuhiro Morisaki¹, Shizue Ueno, Akinori Saeki, Atsushi Asano, Shu Seki, Yoshiki Chujo

Affiliation

¹ Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan. ymo@chujo.synchem.kyoto-u.ac.jp

PMID: 22374648
DOI: 10.1002/chem.201103653

Abstract

[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units.