title: Helicity induction and memory of the macromolecular helicity in a polyacetylene bearing a biphenyl pendant.
abstract: A novel, cis-transoidal poly-(phenylacetylene) bearing a carboxybiphenyl group as the pendant (poly-1) was prepared by polymerization of (4'-ethoxycarbonyl-4-biphenylyl)acetylene with a rhodium catalyst followed by hydrolysis of the ester groups. Upon complexation with various chiral amines and amino alcohols in dimethyl sulfoxide (DMSO), the polymer exhibited characteristic induced circular dichroism (ICD) in the UV/Vis region due to the predominantly one-handed helix formation of the polymer backbone as well as an excess of a single-handed, axially twisted conformation of the pendant biphenyl group. Poly-1 complexed with (R)-2-amino-1-propanol showed unique time-dependent inversion of the macromolecular helicity. Furthermore, the preferred-handed helical conformation of poly-1 induced by a chiral amine was further "memorized" after the chiral amine was replaced with achiral 2-aminoethanol or n-butylamine in DMSO. In sharp contrast to the previously reported memory in poly((4-carboxyphenyl)acetylene), the present helicity memory of poly-1 was accompanied by memory of the twisted biphenyl chirality in the pendants. Unprecedentedly, the helicity memory of poly-1 with achiral 2-aminoethanol was found to occur simultaneously with inversion of the axial chirality of the biphenyl groups followed by memory of the inverted biphenyl chirality, thus showing a significant change in the CD spectral pattern.
authors.affiliation: Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan, Fax: (+81) 52-789-3185.|Present Address: Institute for Advanced Research, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan.
authors.forename: Katsuhiro
authors.initials: K
authors.lastname: Maeda
authors.affiliation: Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan, Fax: (+81) 52-789-3185.
authors.forename: Shinji
authors.initials: S
authors.lastname: Tamaki
authors.affiliation: Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan, Fax: (+81) 52-789-3185.
authors.forename: Kazumi
authors.initials: K
authors.lastname: Tamura
authors.affiliation: Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan, Fax: (+81) 52-789-3185.
authors.forename: Eiji
authors.initials: E
authors.lastname: Yashima