Precise Molecular Fission and Fusion: Quantitative Self-Assembly and Chemistry of a Metallo-Cuboctahedron

Angew Chem Int Ed Engl. 2015 Aug 3;54(32):9224-9. doi: 10.1002/anie.201503609. Epub 2015 Jun 11.

Abstract

Inspiration for molecular design and construction can be derived from mathematically based structures. In the quest for new materials, the adaptation of new building blocks can lead to unexpected results. Towards these ends, the quantitative single-step self-assembly of a shape-persistent, Archimedean-based building block, which generates the largest molecular sphere (a cuboctahedron) that has been unequivocally characterized by synchrotron X-ray analysis, is described. The unique properties of this new construct give rise to a dilution-based transformation into two identical spheres (octahedra) each possessing one half of the molecular weight of the parent structure; concentration of this octahedron reconstitutes the original cuboctahedron. These chemical phenomena are reminiscent of biological fission and fusion processes. The large 6 nm cage structure was further analyzed by 1D and 2D NMR spectroscopy, mass spectrometry, and collision cross-section analysis. New routes to molecular encapsulation can be envisioned.

Keywords: Archimedean polyhedra; self-assembly; shape-persistent macromolecules; supramolecular chemistry.

Publication types

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

MeSH terms

  • Ligands
  • Macromolecular Substances / chemistry*
  • Magnetic Resonance Spectroscopy
  • Metals / chemistry*
  • Nanostructures / chemistry
  • Spectrometry, Mass, Electrospray Ionization

Substances

  • Ligands
  • Macromolecular Substances
  • Metals