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Jasna Alić1, Roman Messner2, Marija Alešković1

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Diamondoid ethers self-assemble within superfluid helium nanodroplets, driven by London dispersion forces. Hydrogen bonding with water, however, leads to aggregate breakdown, revealing complex cluster dynamics.

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Area of Science:

  • Physical Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Superfluid helium nanodroplets offer a unique environment for studying molecular self-assembly.
  • Diamondoid ethers represent a class of molecules with potential applications in materials science.

Purpose of the Study:

  • To investigate the self-assembly behavior of diamondoid ethers in superfluid helium nanodroplets.
  • To determine the driving forces and breakdown mechanisms of diamondoid ether clusters.

Main Methods:

  • Introduction of diamondoid ethers into superfluid helium nanodroplets.
  • Analysis of resulting clusters using time-of-flight mass spectrometry.
  • Computational modeling (GFN2-xTB and DFT) to determine cluster geometries.

Main Results:

  • Identification of magic number clusters indicating stable self-assembled structures.
  • London dispersion forces between hydrocarbon subunits identified as a key driver for cluster formation.
  • Hydrogen bonding between ether oxygens and trace water molecules promotes aggregate dissociation.

Conclusions:

  • Diamondoid ethers exhibit facile self-assembly in helium nanodroplets.
  • The interplay between London dispersion and hydrogen bonding governs the stability and breakdown of these supramolecular aggregates.