Long-range effects of chirality in aromatic poly(isocyanide)s

Abstract

The preparation of optically active atropoisomeric polymers which present chiral backbones, thanks to induction during their synthesis from stereogenic centers, located far away from the skeleton is possible, thanks principally to semirigid conformations of the promesogenic spacers between them. The result is that chiral information can be passed as far as 21 Å from the asymmetric center to the carbon atom that forms the polymeric chain in poly(isocyanide)s. The sense of chiral induction in these conformationally rigid polymers parallels the helical sense of the cholesteric phases, as well as to the helical senses of chiral smectic C phases, induced by the monomers in nematic and smectic C phases, respectively. All these phenomena obey the odd-even rules proposed for chiral sense changes in these liquid crystalline phases. Noncovalent interactions play an important part in the induction process, in which steric arguments can be used to justify the inductions observed. The methodology can be used to prepare macromolecules, which display switching behavior upon thermal or electrochemical stimulus. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3161-3174, 2006