title: Synthesis of complementary double-stranded helical oligomers through chiral and achiral amidinium-carboxylate salt bridges and chiral amplification in their double-helix formation.
abstract: A series of complementary molecular strands from 2-mer to 5-mer that are composed of m-terphenyl units bearing chiral/achiral amidine or achiral carboxyl groups linked via Pt(II) acetylide complexes were synthesized by sequential stepwise reactions, and their chiroptical properties on the double-helix formation were investigated by circular dichroism (CD) and (1)H NMR spectroscopies. In CHCl(3), the "all-chiral" amidine strands consisting of (R)- or (S)-amidine units formed preferred-handed double helices with the complementary achiral carboxylic acid strands through the amidinium-carboxylate salt bridges, resulting in characteristic induced CDs in the Pt(II) acetylide complex regions, indicating that the chiral substituents on the amidine units biased a helical sense preference. The Cotton effect patterns and intensities were highly dependent on the molecular lengths. The complementary double-helix formation was also explored using the chiral/achiral amidine strands with different sequences in which a chiral amidine unit was introduced at the center (center-chiral) or a terminus (edge-chiral) of the amidine strands. The effect of the sequences of the chiral and achiral amidine units on the amplification of chirality (the "sergeants and soldiers" effect) in the double-helix formation was investigated by comparing the CD intensities with those of the corresponding all-chiral amidine double helices with the same molecular lengths. Variable-temperature CD experiments of the all-chiral and chiral/achiral amidine duplexes demonstrated that the Pt(II)-linked complementary duplexes are dynamic and their chiroptical properties including the chirality transfer from the chiral amidine unit to the achiral amidine ones are significantly affected by the molecular lengths, sequences, and temperatures. On the basis of the above results together with molecular dynamics simulation results, key structural features of the Pt(II)-linked oligomer duplexes and the effect of the chiral/achiral amidine sequences on the amplification of chirality are discussed.
authors.affiliation: Yashima Super-structured Helix Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Ito
authors.forename: Masato
authors.initials: M
authors.lastname: Ikeda
authors.forename: Takashi
authors.initials: T
authors.lastname: Hasegawa
authors.forename: Yoshio
authors.initials: Y
authors.lastname: Furusho
authors.forename: Eiji
authors.initials: E
authors.lastname: Yashima
mesh_terms: D000578:Amidines / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002942:Circular Dichroism; D004247:DNA / Q000138:chemical synthesis* / Q000737:chemistry / Q000235:genetics; D019906:Nuclear Magnetic Resonance, Biomolecular; D009690:Nucleic Acid Conformation; D013237:Stereoisomerism
chemical_list: D000578:Amidines; D002264:Carboxylic Acids; D004247:DNA