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Coverage-modulated halogen bond geometry transformation in supramolecular assemblies.

Alejandro Jiménez-Martín1,2,3, Aurelio Gallardo3,4, Bruno de la Torre1,3

  • 1Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacký University Olomouc, 78371 Olomouc, Czech Republic. bruno.de@upol.cz.

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|October 3, 2023
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This summary is machine-generated.

Researchers developed a new method to control molecular self-assembly on surfaces using halogen bonding (HB). This strategy tunes the directionality of interactions, enabling the creation of one-dimensional and two-dimensional structures for advanced materials.

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Area of Science:

  • Supramolecular chemistry
  • Surface science
  • Organic electronics

Background:

  • Halogen bonding (HB) offers directional interactions for designing supramolecular assemblies.
  • Tuning HB directionality on inert metal surfaces remains a challenge.
  • Understanding molecular assembly on surfaces is crucial for functional materials.

Purpose of the Study:

  • To present a strategy for tuning the directionality of homomolecular organic compound self-assembly on inert metal surfaces.
  • To investigate the influence of molecular coverage on self-assembly structures.
  • To explore the potential of HB assemblies in confining electronic states and atoms.

Main Methods:

  • High-resolution atomic force microscopy (AFM) for experimental structural analysis.
  • First-principle calculations, including density functional theory (DFT), to model interactions.
  • Controlled variation of molecular coverage on Au(111) surfaces.

Main Results:

  • Achieved tunable one-dimensional (1D) and two-dimensional (2D) self-assembly based on molecular coverage.
  • Observed a transformation from type-I to synthon halogen bonding, forming hexagonal patterns.
  • Demonstrated confinement of electronic quantum states and single atoms by HB supramolecular assemblies.

Conclusions:

  • The study presents a versatile strategy for controlling molecular self-assembly directionality on inert metal surfaces via halogen bonding.
  • A balance of electrostatic and dispersion forces drives the observed halogen-bond geometry transformation.
  • The findings offer new possibilities for designing functional molecular architectures on substrates.