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Approaching Materials with Atomic Precision Using Supramolecular Cluster Assemblies.

Papri Chakraborty1, Abhijit Nag1, Amrita Chakraborty1

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This study explores supramolecular chemistry in atomically precise nanoclusters (NCs), revealing how non-covalent interactions drive the formation of complex assemblies and hybrid materials with tunable properties.

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Area of Science:

  • Supramolecular Chemistry
  • Nanocluster Science
  • Materials Science

Background:

  • Supramolecular chemistry leverages non-covalent interactions (hydrogen bonding, van der Waals, electrostatic, π···π, C-H···π) for molecular self-assembly.
  • Atomically precise nanoclusters (NCs) exhibit molecular behavior, enabling exploration of their supramolecular chemistry.
  • Precise NC assemblies can lead to novel cluster-assembled hybrid materials with tailored properties.

Purpose of the Study:

  • To review recent advancements in supramolecular interactions within atomically precise cluster systems.
  • To discuss the formation and characterization of various NC-based supramolecular assemblies and hybrid materials.
  • To highlight the role of non-covalent interactions in controlling the structure and properties of these advanced materials.

Main Methods:

  • Electrospray ionization mass spectrometry (ESI MS) for adduct formation analysis.
  • Optical absorption and NMR spectroscopy for characterization.
  • Single-crystal X-ray diffraction for studying polymorphic crystals.
  • Transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), and 3D tomographic reconstructions for hybrid assembly analysis.

Main Results:

  • Demonstrated supramolecular interactions between NCs and guests like cyclodextrins and fullerenes.
  • Observed polymorphic crystal formation driven by intercluster interactions (C-H···π, π···π).
  • Fabricated precision hybrid assemblies of NCs with tellurium nanowires and encapsulated nanorods, controlled by ligand geometry and hydrogen bonding.

Conclusions:

  • Supramolecular interactions are crucial for precise assembly of NCs into complex architectures.
  • Ligand design and non-covalent forces dictate the formation of hybrid materials with unique structures.
  • The integration of molecular and structural tools is key to advancing cluster supramolecular chemistry for new material development.