Different phase-dominated chiral assembly of polyfluorenes induced by chiral solvation: axial and supramolecular chirality

Abstract

The introduction of chirality in an achiral system will not only help avoid the tedious and expensive synthesis of chiral substances or catalysts but also greatly expand the ranges of chiral compounds. Herein, the induction of chirality in achiral polyfluorene (PF2/6 and PF8) with different alkyl chains at the C9 position of fluorene was achieved using a binary solvent system, in which ethanol was used as a poor solvent and chiral limonene was employed simultaneously as a good solvent and chiral solvent. The circular dichroism (CD), UV-vis and photoluminescence (PL) spectra demonstrated that the structures of PFs with linear/branched alkyl side chains and the volume fractions of the cosolvents had an obvious effect on the generation of chirality driven by chiral solvation. During the chiral assembly processes of PFs, PF8 with a linear alkyl side chain demonstrated the obvious chiral β phase, while PF2/6 with a branched alkyl side chain only showed the chiral α phase. WAXD data also confirmed the existence of quite different phases of PF8 and PF2/6. The first induced chirality of PF with a branched alkyl side chain (PF2/6) will help the further understanding of the chiral assembly mechanism of PFs driven by chiral solvation. The induced chirality of PF2/6 was axial chirality of the PF chain but the chirality of PF8 was from the supramolecular chiral assembly of the PF chains. The linear dependence of the maximum CD and g_CD values on the enantiomeric purity of chiral limonene demonstrated that the achiral PFs have a potential application as chiral sensors to detect the ee value of limonene.