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Cluster self-assembly of di[gold(I)]halonium cations
Hubert Schmidbaur1, Armin Hamel, Norbert W Mitzel
1Anorganisch-Chemisches Institut, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany. h.schmidbaur@lrz.tum.de
Summary
Gold(I) halide complexes self-assemble into novel tetranuclear dications via aurophilic gold-gold interactions. These interactions are significant in crystal lattices with large ionic radius anions, demonstrating dependable intermetallic bonding.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Crystal Engineering
Background:
- Gold(I) complexes are known to exhibit interesting structural motifs.
- Aurophilic interactions, or gold-gold bonding, are weak but significant in stabilizing structures.
Purpose of the Study:
- To synthesize and characterize novel gold(I) halonium salts.
- To investigate the self-assembly of these salts into larger structures.
- To explore the role of aurophilic interactions in crystal packing.
Main Methods:
- Treatment of gold(I) halide complexes with silver hexafluoridophosphate.
- Crystallization and X-ray diffraction analysis of the resulting salts.
- Structural comparison with related gold(I) compounds.
Main Results:
- High yields of di[gold(I)]halonium salts were obtained.
- Novel tetranuclear dications with S(4) symmetry were discovered, formed by self-assembly of dinuclear monocations.
- Aurophilic Au-Au interactions were identified as the driving force for self-assembly.
- The significance of aurophilic bonding is enhanced by larger counteranions (SbF(6)(-)) compared to smaller ones (BF(4)(-), ClO(4)(-)).
Conclusions:
- Gold(I) halide complexes can self-assemble into complex tetranuclear structures driven by aurophilic interactions.
- The strength and observability of aurophilic bonding are influenced by the crystal lattice environment, particularly the size of the counteranion.
- Aurophilic interactions are a reliable mode of intermetallic bonding when conditions favor their operation.