Synthesis and conformation of substituted chiral binaphthyl-azobenzene cyclic dyads with chiroptical switching capabilities

Molecules. 2011 Feb 14;16(2):1603-24. doi: 10.3390/molecules16021603.

Abstract

Optically active binaphthyl-azobenezene cyclic dyads were synthesized to develop a photochromic switching molecule. Azobenezene moieties were cis-trans isomerized by photoirradiation. As a reflection of the structural change, the specific optical rotation and circular dichroism underwent significant shifts. Under certain conditions, the positive-negative and zero-positive (or zero-negative) signals were reversed. Optical rotation may potentially be applied in noise-cancelling nondestructive photoswiches. The conformations were studied by experimental and theoretical methods. The results revealed that the helical chirality, (P) or (M), of the cis-azobenzene moiety was induced by intramolecular axial chirality. The twist direction depended on the axial chirality as well as the azobenzene linkage position to the binaphthyls, but was independent of the identity of substituted groups. 2,2'-Linked-(R)-binaphthyl was found to induce cis-(P)-azobenzene, whereas symmetrically 7,7'-linked-(R)-binaphthyl was found to induce cis-(M)-azobenzene.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Azo Compounds / chemical synthesis*
  • Azo Compounds / chemistry*
  • Circular Dichroism
  • Hydrocarbons, Cyclic / chemical synthesis*
  • Hydrocarbons, Cyclic / chemistry*
  • Molecular Conformation
  • Molecular Structure
  • Optical Rotation
  • Stereoisomerism
  • Thermodynamics

Substances

  • Azo Compounds
  • Hydrocarbons, Cyclic
  • azobenzene