Anomalous Chiral Transfer: Supramolecular Polymerization in a Chiral Medium of a Mesogenic Molecule.

Here, we report a medium-to-polymer anomalous chiral transfer in the supramolecular polymerization of a tetraphenylporphyrin-based achiral hydrogen-bonding monomer (TPP) in a chiral medium of 5-cyanobiphenyl CB*. A mixture of TPP in (R)-CB* ([TPP]=7.7 mol %) at 40 °C gave a columnar oblique LC mesophase, where the individual columns were composed of an optically active helical supramolecular polymer of TPP as a consequence of a successful medium-to-polymer chiral transfer. Meanwhile, upon dilution of CB* with achiral 5-cyanobiphenyl CB, the optical activity of the system showed an anomalous bell-shaped dependency on the composition of CB*/CB, where the g abs value of 0.049 at CB*/CB=50/50 was 6.0 times larger than the g abs value of CB* alone. Such anomalous chiroptical amplification in CD is most likely due to a change in the stacking geometry of TPP in the oblique columnar LC upon lateral compression.