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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies
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Structural basis for ligand exchange on Au(25)(SR)(18).

Thomas W Ni1, Marcus A Tofanelli, Billy D Phillips

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|June 24, 2014
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Summary
This summary is machine-generated.

Ligand exchange on gold nanoclusters (Au25) was structurally resolved for the first time. This study reveals the exchange occurs at the most exposed gold atom, supporting an associative mechanism for ligand substitution.

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Area of Science:

  • Nanochemistry
  • Crystallography
  • Surface Science

Background:

  • The Au25(SR)18 cluster is a widely studied gold nanocluster.
  • Ligand exchange is a common method for functionalizing gold nanoclusters.
  • Structural elucidation of ligand exchange mechanisms is crucial for controlling nanocluster properties.

Purpose of the Study:

  • To present the single-crystal X-ray structure of a ligand-exchanged gold nanocluster, Au25(SC2H4Ph)16(pBBT)2.
  • To structurally resolve the ligand exchange process on the Au25(SR)18 core for the first time.
  • To investigate the mechanism of ligand exchange in gold nanoclusters.

Main Methods:

  • Single-crystal X-ray diffraction
  • Ligand exchange reaction
  • Crystallographic analysis

Main Results:

  • The structure of Au25(SC2H4Ph)16(pBBT)2 was determined.
  • A single ligand exchange event was observed in the asymmetric unit, corresponding to two ligands per molecule due to symmetry.
  • The exchanged ligand is attached to the most solvent-exposed gold atom, consistent with an associative mechanism.
  • Non-exchange of other ligands is attributed to selective crystallization and differential bond lengths.

Conclusions:

  • Ligand exchange on Au25(SR)18 clusters can be structurally resolved.
  • The observed ligand exchange proceeds via an associative mechanism.
  • Selective crystallization plays a role in the observed product distribution.