A supramolecular helix that disregards chirality

Nat Chem. 2016 Jan;8(1):80-9. doi: 10.1038/nchem.2397. Epub 2015 Nov 16.

Abstract

The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Circular Dichroism
  • Crystallization
  • Imides / chemical synthesis*
  • Imides / chemistry*
  • Macromolecular Substances
  • Magnetic Resonance Spectroscopy
  • Models, Molecular*
  • Molecular Structure
  • Perylene / analogs & derivatives*
  • Perylene / chemical synthesis
  • Perylene / chemistry
  • Phase Transition
  • Solutions
  • Spectrophotometry, Ultraviolet
  • Stereoisomerism
  • X-Ray Diffraction

Substances

  • Imides
  • Macromolecular Substances
  • Solutions
  • perylene bisimide
  • Perylene

Associated data

  • PubChem-Substance/253658137
  • PubChem-Substance/253658138
  • PubChem-Substance/253658139
  • PubChem-Substance/253658140
  • PubChem-Substance/253658141
  • PubChem-Substance/253658142
  • PubChem-Substance/253658143
  • PubChem-Substance/253658144
  • PubChem-Substance/253658145
  • PubChem-Substance/253658146
  • PubChem-Substance/253658147
  • PubChem-Substance/253658148
  • PubChem-Substance/253658149
  • PubChem-Substance/253658150
  • PubChem-Substance/253658151
  • PubChem-Substance/253658152
  • PubChem-Substance/253658153
  • PubChem-Substance/253658154