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Helix Induction to Polyfluorenes Using Circularly Polarized Light: Chirality Amplification, Phase-Selective Induction, and Anisotropic Emission
- Wang, Yue, Harada, Takunori, Phuong, Le Quang, Kanemitsu, Yoshihiko, Nakano, Tamaki
- Macromolecules 2018 v.51 no.17 pp. 6865-6877
- absorbance, ambient temperature, anisotropy, irradiation, light intensity, luminescence, optical isomerism, photochemical reactions, polymers, storage temperature, wavelengths
- Chirality induction (preferred-handed helix induction) to poly(9,9-dioctylfluorene-2,7-diyl) (poly(DOF)), poly(9,9-didodecylfluorene-2,7-diyl) (poly(DDF)), and poly(9,9-dihexylfluorene-2,7-diyl) (poly(DHF)) using circularly polarized light (CPL) was thoroughly investigated mainly using film samples. We found that the presence of the β-phase is indispensable in chirality induction to poly(DOF) which suggests the importance of interchain interactions and that chirality induction first occurs preferentially in the β-phase and then extended to the α-phase. Chirality induction only to the β-phase was attained by irradiating at the β-phase absorbance band (435 nm) or by irradiating the full wavelength range for a short time while pure α-phase chirality is induced for poly(DHF) having no β-phase using an achiral aid molecule. Chirality induction is feasible for polymers having octyl and dodecyl chains, poly(DOF) and poly(DDF), whereas it is not possible for the polymer having a hexyl chain, poly(DHF), unless an aid molecule is used. CPL-driven chirality induction occurs through enantiomer-selective photoexcitation of either a right- and left-handed twisted diad composing the polymer chain into achiral, coplanar conformation, and deactivation of the coplanar conformation leading to right- and left-handed twisted diads. Chirality amplification takes place through biased deactivation of coplanar conformation preferentially to the hand which is the same as that of “preformed single-handed diad or longer chain” in the vicinity (“deactivation chirality amplification”). In addition, “ground-state chirality amplification” is also proposed on the basis of significant temperature effects in chirality induction. Chiral structure induced to the film samples is stable if they are stored at room temperature without irradiation with intense light. Optically active poly(DOF) films showed efficient circularly polarized luminescence.