Two-Dimensional Bilayer Smectic Ordering of Rigid Rod−Rod Helical Diblock Polyisocyanides

The rigid-rod-like left-handed helical polyisocyanides (poly-3) with a different molecular weight and a narrow molecular weight distribution were prepared by the living polymerization of an enantiomerically pure phenyl isocyanide bearing an l-alanine pendant with an n-hexyl chain (3) using the μ-ethynediyl Pt−Pd catalyst. The left-handed helical poly-3s maintain their living feature and further copolymerized an analogous l-alanine-bound phenyl isocyanide with a long n-tetradecyl chain (4) to produce rod−rod diblock polyisocyanides with a controlled helical sense and a narrow molecular weight distribution. The rigid rod−rod helical diblock copolyisocyanides were composed of the same l-alanine pendants, but with alkyl chains of different lengths self-assembled to form the nanometer-scaled bilayer smectic-like ordering on a substrate and in a liquid crystalline state as evidenced by the direct atomic force microscopic and polarized optical micrograph observations, respectively.