Self-Assembly through Noncovalent Preorganization of Reactants: Explaining the Formation of a Polyfluoroxometalate

Roy E. Schreiber, Liat Avram, Ronny Neumann

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)


High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H2F6NaW18O56]7− from simple tungstate Na2WO2F4 was demonstrated by using 2D 19F–19F NOESY, 2D 19F–19F COSY NMR spectroscopy, a new 2D 19F{183W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions.

Original languageEnglish
Pages (from-to)369-379
Number of pages11
JournalChemistry - A European Journal
Issue number2
Publication statusPublished - Jan 9 2018


  • NMR spectroscopy
  • mass spectrometry
  • polyoxometalates
  • self-assembly
  • tungsten

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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