Here, we report the mechanisms of chiral transfer at various length scales in the self-assembly of enantiomeric chiral block copolymers (BCPs*). We show the evolution of homochirality from molecular chirality into phase chirality in the self-assembly of the BCPs*. The chirality of the molecule in the BCP* is identified from circular dichroism (CD) spectra, while the handedness of the helical conformation in the BCP* is determined from a split-type Cotton effect in vibrational circular dichroism spectra. Microphase separation of the BCP* is exploited to form a helical (H*) phase, and the handedness of helical nanostructure in the BCP* is directly visualized from transmission electron microscopy tomography. As examined by CD and fluorescence experiments, significant induced CD signals and a bathochromic shift of fluorescence emission for the achiral perylene moiety as a chemical junction of the BCPs* can be found while the concentration of the BCPs* in toluene solution is higher than the critical micelle concentration, suggesting a twisting and shifting mechanism initiating from the microphase-separated interface of the BCPs* leading to formation of the H* phase from self-assembly.
Banded spherulites are formed by crystallization of a chiral polymer that is end-capped with chromophore. Induced circular dichroism (ICD) of the chromophore can be found in the crystallized chiral polymers, giving exclusive optical response of the ICD. The ICD signals are presumed to be driven by the lamellar twisting in the crystalline spherulites, and the exclusive optical activity is attributed to the chirality transfer from molecular level to macroscopic level. To verify the suggested mechanism, the sense of the lamellar twisting in the crystalline spherulite is determined using PLM for the comparison with the ICD signals of the chromophore in the electron circular dichroism spectrum. The conformational chirality of the chiral polymer is determined by the vibrational circular dichroism spectrum. On the basis of the chiroptical results, evolution of homochirality from helical polymer chains (conformational chirality) to lamellar twisting in the banded spherulite (hierachical chirality) is suggested.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.