Abstract: | Homogeneous and high‐quality free‐standing poly(1,6‐bis(carbazolyl) hexane) (P2Cz‐H) and poly(1,12‐bis(carbazolyl)dodecane) (P2Cz‐D) films were electrochemically synthesized in CH2Cl2 + 0.1 M tetrabutylammonium tetrafluoroborate solution. The electrochemical and physical properties indicated that the quality of P2Cz‐D film with tensile strength of 165 kg cm−2 was better than that of P2Cz‐H due to the flexible monomer 1,12‐bis(carbazolyl)dodecane (2Cz‐D) has a longer carbon chain than that of monomer 1,6‐bis(carbazolyl)hexane (2Cz‐H). On the other hand, both the dicarbazole monomers showed better polymer‐film‐forming capabilities than the single carbazole monomer, partly because of the special design of the polymer backbone constituted of stiff bicarbazyl chromophores linked by flexible long carbon segments. The structures of both dicarbazole polymers were investigated by UV–visible, infrared spectroscopy and scanning electron microscopy. Fluorescence spectral studies revealed that the two dedoped polymer films in solid state had strong emissions at ca. 411 and 415 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5232–5241, 2008 |