Matched and Mismatched Phenomena in the Helix Orientation Bias Induced by Chiral Appendages at Multiple Positions of Indolocarbazole-Pyridine Hybrid Foldamers

A series of indolocarbazole-pyridine (IP) hybrid foldamers containing chiral residues at multiple different positions were prepared to reveal the matched and mismatched phenomena of local stereocenters on the induction of helical bias. These foldamers adopted stable helical conformations, thus affording well-resolved separate sets of ¹H NMR signals for right- (P) and left-handed (M) helices in water saturated organic solvents such as toluene and dichloromethane. The ratios of P- and M-helices were determined by integrating the ¹H NMR signals, in combination with the molar circular dichroism (Δ ϵ) and optical rotation ([α]_D) values. The degree of helical bias was larger in the IP foldamer bearing chiral residues at the termini relative to those at the pyridine side chains, but the preferred helix orientation was opposite to each other. Foldamers 5^(SS)t(SSS)py and 6^(RR)t(SSS)py with chiral residues at five different positions demonstrated the matched and mismatched phenomena of local stereocenters in 6^(RR)t(SSS)py and 5^(SS)t(SSS)py, respectively.