Toward controlled donor-acceptor interactions in noncomposite polymeric materials: Synthesis and characterization of a novel polythiophene incorporating pi-conjugated 1,3-dithiole-2-ylidenefluorene units as strong D-A components

A novel polythiophene bearing a strong electron-accepting fluorene unit has been synthesized. Poly(2d) can be prepared by chemical (iron(III) chloride ) or electrochemical oxidation. Intramolecular charge-transfer (ICT) within the polymer was studied by electronic absorption spectroscopy and compared to a series of model monomer derivatives. The redox properties of the mate rials were studied by cyclic voltammetry; polythiophene main chain in poly( 2d) is oxidized at ca. +0.7 V vs Ag/AgCl, while the nitrofluorene repeat un it is reduced at ca. -0.5 and -0.7 V. The model compounds 3a-e show a Hamme tt-type correlation for ICT energies, E-1red(1/2) and E-2red(1/2) vs the su bstituents on the fluorene ring, with the sensitivity parameters rho (ICT)- approximate to 0.17-0.20 eV and rho (CV)- approximate to 0.17-0.25 V. In c ontrast, the oxidation process (E-OX) displays very low sensitivity to the structure of the fluorene ring (rho (CV)- approximate to 0.04 V), indicatin g that ICT can be substantially tuned without a noticeable effect on the re dox properties of the thiophene moiety in 3; this behavior can be extended. (extrapolated) to terthiophenes 2 and their polymers. Photoinduced IR spec troscopy of poly(2d) provides evidence of long-living photoexcited charge t ransfer in the polymer.