Helical Polyguanidines Prepared by Helix-Sense-Selective Polymerizations of Achiral Carbodiimides Using Enantiopure Binaphthol-Based Titanium Catalysts

Abstract

The polymerization of N-(n-hexyl)-N‘-phenylcarbodiimide was studied using a number of homochiral catalysts based on binaphthol derivatives. All polymers showed optical activity due to the formation of a predominant screw sense controlled by the chirality of the catalyst. The helicity and chirality of these materials were studied by VCD, ECD, and polarimetry. Structures calculated using density functional theory were used to compare with their simulated VCD and experimental VCD, thus allowing the absolute screw sense to be determined. AFM imaging showed epitaxial ordering of these rigid chains on graphite surfaces and single chains measuring nearly 3 mm were observed in spin-cast samples on silicon.