The structural diversity triggered by intermolecular interactions between Au(I)S2 groups: aurophilia and beyond
Mohammad-Reza Azani1, Oscar Castillo, M Luz Gallego
1Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 12, 2012
Summary
This study reveals how gold(I) species assemble with ligands, forming diverse structures in crystals but discrete bimetallic units in solution. Dithiocarboxylato ligands enable reversible supramolecular assembly, influencing luminescent properties.
Area of Science:
- Inorganic Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Gold(I) complexes exhibit diverse structural behavior.
- Ligand choice significantly impacts the assembly of metal centers.
- Understanding self-assembly is crucial for designing functional materials.
Purpose of the Study:
- To elucidate factors governing the assembly of gold(I) species.
- To investigate the structural diversity arising from gold(I) and dithiocarboxylato/xanthato ligands.
- To explore the luminescent properties and driving forces of assembled gold(I) complexes.
Main Methods:
- Single-crystal X-ray diffraction for structural determination.
- Solution-state characterization of gold(I) species.
- Variable temperature luminescence studies.
- Computational modeling (DFT) to analyze interactions.
Main Results:
- Surprising structural diversity observed in solid-state gold(I) assemblies.
- Discrete bimetallic [Au(2)L(2)] species identified in solution.
- Reversible supramolecular assembly ([Au(2)L(2)](2) and [Au(2)L(2)](3)) formed with dithiocarboxylato ligands.
- Solid-state compounds exhibit red emissions, suggesting intramolecular interactions dominate luminescence.
Conclusions:
- Ligand type dictates the assembly pathway of gold(I) complexes.
- Intramolecular interactions are key to the luminescent properties of these gold(I) supramolecular species.
- Computational studies highlight the role of Au-Au, Au-S, and S-S interactions in assembly and energetics.
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