Ligand and Metal Exchanges between [(AuAg)44(SR)30]4- Clusters via Bimolecular Superatomic Collision
Hai-Feng Su1, Hongwen Deng1, Lan-Sun Zheng1
1State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Inorganic Chemistry
|May 19, 2025
Summary
Ligand exchange in gold-silver nanoclusters is instant, while metal exchange is slow, occurring in the cluster core. Both processes require bimolecular collisions between nanoclusters.
Area of Science:
- Nanomaterials Science
- Inorganic Chemistry
- Physical Chemistry
Background:
- Superatomic clusters like [(AuAg)44(SR)30]4- exhibit unique properties due to their discrete electronic structures.
- Understanding intercluster reactions is crucial for designing novel nanomaterials with tailored functionalities.
Purpose of the Study:
- To investigate the mechanisms of ligand and metal exchange reactions between [(AuAg)44(SR)30]4- nanoclusters.
- To elucidate the kinetics and collision requirements for these intercluster exchange processes.
Main Methods:
- Electrospray ionization mass spectrometry (ESI-MS) for mass analysis.
- X-ray crystallography for structural determination.
- UV-vis spectroscopy for electronic property monitoring.
Main Results:
- Ligand exchange reactions are rapid and follow a random substitution pattern (Gaussian distribution).
- Metal (Au-Ag) exchange reactions are slow, yielding fractal patterns and occurring within the icosahedral core.
- Reactions require bimolecular collisions, evidenced by experiments with permeable membranes and the observation of transient dimer intermediates.
Conclusions:
- Intercluster ligand and metal exchange in gold-silver nanoclusters are distinct processes with different kinetics.
- Both exchange types necessitate direct contact and bimolecular collisions between superatomic clusters.
- The findings provide insights into the dynamic behavior and reaction pathways of complex metal nanoclusters.
More Related Videos
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
9.1K
03:54Author Spotlight: Designing Sustainable Nanomaterials for Advancing Synthesis and Element Mixing
Published on: March 15, 2024
721
Related Concept Videos
02:51Metal-Ligand Bonds
20.4K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
20.4K
01:19Complexation Equilibria: The Chelate Effect
416
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
416
00:56Extraction: Advanced Methods
398
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
398
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
313
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
313
03:45Formation of Complex Ions
23.1K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
23.1K
00:43Complexometric Titration: Ligands
864
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
864