Encapsulating Iodine and Copper into Copper(I) Clusters Stabilized by Dichalcogenolate Ligands: Stability, Structure,...

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Large copper(I) clusters offer unique structural and electronic properties.
• Encapsulation of anions within metal clusters is an area of active research.
• Understanding bonding and photoluminescence in these systems is crucial for potential applications.

Purpose of the Study:

• To investigate the stability and electronic properties of large ligated copper(I) clusters.
• To explore the photoluminescent characteristics of these clusters using theoretical methods.
• To compare computational findings with experimental data for synthesized copper(I) iodide clusters.

Main Methods:

• Density functional theory (DFT) calculations for stability and bonding analysis.
• Time-dependent DFT (TD-DFT) calculations with vibronic contributions to simulate spectra.
• Synthesis, X-ray structure determination, and characterization of novel copper(I) clusters.

Main Results:

• Strong iono-covalent bonding was observed between iodide and the copper(I) host.
• Electronic structures suggest potential for significant photoluminescent properties.
• Experimental data for [Cu11(μ9-I)(μ3-I)3{Se2P(OiPr)2}6]+ and [Cu11(μ9-I)(μ3-I)3(Se2PPh2)6]+ clusters validated DFT predictions.
• The possibility of encapsulating a Cu- anion, forming stable two-electron superatoms, was computationally supported.

Conclusions:

• The investigated copper(I) clusters are stable and possess interesting electronic and photoluminescent properties.
• Combined theoretical and experimental approaches provide a comprehensive understanding of these complex systems.
• The findings suggest potential for further exploration of superatom chemistry within copper clusters.