Encapsulation of chiral guests in the dissymmetric capsule 1⋅4 BF4 formed diastereomeric supramolecular complexes G⊂1⋅4 BF4 (G: guest). When chiral guests 2 a-q were encapsulated within the dissymmetric space of the self-assembled capsule 1⋅4 BF4 , circular dichroism (CD) was observed at the absorption bands that are characteristic of the π-π* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)-2 l⊂1⋅4 BF4 was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j. The relative enthalpic and entropic components for the distereoselectivity were obtained from a van't Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (σp (+) ). The electron-rich benzyl ester moieties generated donor-acceptor π-π stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes.

Repeating guest units of polyesters poly-(R)-2 were selectively encapsulated by capsule 1(BF ) to produce supramolecular graft polymers. The encapsulation of the guest units was confirmed by H NMR spectroscopy. The graft polymer structures were confirmed by the increase in the hydrodynamic radii and the solution viscosities of the polyesters upon complexation of the capsule. After the capsule was formed, atomic force microscopy showed extension of the polyester chains. The introduction of the graft chains onto poly-(R)-2 resulted in the main chain of the polymer having an M-helical morphology. The complexation of copolymers poly-[(R)-2-co-(S)-2] by the capsule gave rise to the unique chiral amplification known as the majority-rules effect.

Encapsulation of chiral guests in the dissymmetric capsule 1·4 BF 4 formed diastereomeric supramolecular complexes G&1·4 BF 4 (G: guest). When chiral guests 2 a-q were encapsulated within the dissymmetric space of the selfassembled capsule 1·4 BF 4 , circular dichroism (CD) was observed at the absorption bands that are characteristic of the p-p* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)-2 l&1·4 BF 4 was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j. The relative enthalpic and entropic components for the distereoselectivity were obtained from a vant Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (s p + ). The electron-rich benzyl ester moieties generated donor-acceptor p-p stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes.

Repeating guest units of polyesters poly-(R)-2 were selectively encapsulated by capsule 1(BF 4 ) 4 to produce supramolecular graft polymers.The encapsulation of the guest units was confirmed by 1 HNMR spectroscopy. The graft polymer structures were confirmed by the increase in the hydrodynamic radii and the solution viscosities of the polyesters upon complexation of the capsule.A fter the capsule was formed, atomic force microscopys howed extension of the polyester chains.T he introduction of the graft chains onto poly-(R)-2 resulted in the main chain of the polymer having an M-helical morphology.The complexation of copolymers poly-[(R)-2-co-(S)-2]b ythe capsule gave rise to the unique chiral amplification knownasthe majority-rules effect.[a] Determined by size-exclusion chromatography.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.