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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Published on: September 26, 2016

Supramolecular porphyrin polymers in solution and at the solid-liquid interface.

Richard van Hameren1, Arend M van Buul, Maria A Castriciano

  • 1Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands.

Nano Letters
|December 7, 2007
PubMed
Summary

Chiral porphyrin trimers form long, chiral supramolecular polymers in nonpolar solvents, precipitating as fibers. In chloroform, they form ordered columnar stacks on mica during spinodal dewetting.

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Physical Chemistry

Background:

  • Chiral molecules exhibit unique self-assembly properties.
  • Understanding molecular self-assembly is crucial for designing advanced materials.
  • Porphyrin trimers are versatile building blocks for supramolecular structures.

Purpose of the Study:

  • To investigate the solvent-dependent self-assembly of a chiral porphyrin trimer.
  • To correlate solution self-assembly with interfacial aggregation behavior.
  • To explore the formation of ordered nanostructures at the solid-liquid interface.

Main Methods:

  • Circular Dichroism (CD) spectroscopy
  • Dynamic and static light scattering
  • Drop-casting onto mica surfaces
  • Atomic Force Microscopy (AFM) implied by "single molecule thick columnar stacks"

Main Results:

  • In n-hexane and cyclohexane, porphyrin trimers self-assemble into chiral supramolecular polymers at micromolar concentrations.
  • These polymers precipitate as fibers upon drop-casting onto mica.
  • In chloroform, the trimer remains molecularly dissolved up to 0.2 mM.
  • Drop-casting of micromolar chloroform solutions onto mica leads to the formation of equidistant lines of single-molecule-thick columnar stacks during spinodal dewetting.

Conclusions:

  • Solvent polarity significantly dictates the self-assembly pathway of chiral porphyrin trimers.
  • Controlled interfacial self-assembly can yield ordered nanostructures like columnar stacks.
  • The study demonstrates a method for fabricating molecularly ordered materials via solvent-controlled interfacial assembly.