Abstract:
Achiral (4-(dodecyloxy)-4'-ethynyl-1,1'-biphenyl-3,5-diyl) dimethanol (PhDHPA) was synthesized, and then was polymerized under the cataysis of an achiral rhodium catalyst, the chemical structures of intermediate compounds and PhDHPA monomer were characterized by nuclear magnetic resonance spectroscopy (
1H-NMR), and the molecular weight and dispersion coefficient of the Poly(PhDHPA) were determined by gel permeation chromatography (GPC). The resulting Poly(PhDHPA) was achiral, however, when chiral bias such as
R-(+)-1-phenylethanol,
S-(-)-dimethyl-1-butanal,
L-menthol, and
R-phenylethylamine, was added in the solution of Poly(PhDHPA), it showed clear circular dichroism (CD) signals in the absorption regions of the polyphenylacetylenes backbones. The sign and pattern of the induced CD signals showed the dependence on the type of chiral bias and the solvent in the system. These indicate that one-handed helix structure could be successfully induced on the main chain of Poly(PhDHPA) by the chiral bias. The chiral induction might be due to the inter-molecular hydrogen bonds or π-π stacking interactions between the polymer with the chiral bias. It is interesting that merely change the solvent caused the helix inversion of the polymer even under the same chiral bias, and the influences of solvent and chiral bias on the induced helical structure of Poly(PhDHPA) in the solution were systematically investigated. The CD-UV/Vis spectra of Poly(PhDHPA)/
L-menthol in different solvents was performed at the temperature region from −10 ℃ to 50 ℃, indicating that the helical structure induced by
L-menthol showed good thermostability.