Optically active fluoro-substituted polyaniline prepared in organic media: The synthesis, chiroptical properties, and comparison with optically active non-substituted polyaniline

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Optically active polyaniline (PANI) bearing an electron-withdrawing fluorine substituent, poly(2-fluoroaniline) (F-PANI), was synthesized in organic solvents by using (+)- or (−)-camphorsulfonic acid (CSA) as a chiral dopant, in which 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) was used as an electron acceptor. Formations of the optically active (chiral) F-PANI/(+)- or (−)-CSA, the dedoped F-PANI, and the redoped F-PANI/CSA were confirmed by the FT-IR, UV/vis/near-IR, and/or circular dichroism (CD) spectroscopy. The CD spectra of the chiral F-PANIs/(+)- and (−)-CSA were investigated in various organic solvents and compared with those of non-substituted PANI/(+)- or (−)-CSA. The F-PANI/(+)-CSA and PANI/(+)-CSA interestingly indicated almost mirror-imaged CD spectra in the visible region, although CD absorptions of the F-PANI/CSA were slightly blue shifted compared with those of PANI/CSA. The chiral F-PANI/CSA was unexpectedly confirmed to remain the initial chiral conformation during reversible dedoping/redoping cycles in solution state. The chiroptical properties of F-PANI/(+)-CSA in organic solvents were found to be affected by the solvent, probably due to the solvent effect to the polymer backbone, and the helical conformation was drastically reversed by change of the solvent. Furthermore, the conformation of F-PANI/CSA in m-cresol can be significantly changed when the F-PANI/CSA was dissolved in cosolvent of m-cresol and DMSO at various volume ratios, in which the sign inversions of CD absorption bands were caused when the ratio of DMSO in the m-cresol/DMSO cosolvent exceeded 10%. On the other hand, in the case with PANI/(+)-CSA, the similar sign inversions of CD absorption bands were not observed under the similar conditions, and then the helical conformation of chiral F-PANI/CSA was supposed to be rather flexible compared with that of chiral PANI/CSA, presumably due to relatively weak interaction among F-PANI backbone, CSA, and m-cresol.