Multinuclear copper(I) and silver(I) amidinate complexes: synthesis, luminescence, and CS2 insertion reactivity

Area of Science:

• Coordination Chemistry
• Organometallic Chemistry
• Luminescence Chemistry

Background:

• Dinuclear copper(I) and silver(I) amidinate complexes were synthesized.
• Amidinate ligands provide a versatile platform for metal complexation.

Purpose of the Study:

• To synthesize novel dinuclear Cu(I) and Ag(I) amidinate complexes.
• To investigate the reactivity of these complexes with carbon disulfide.
• To explore the luminescent properties and oxygen sensitivity of the resulting complexes.

Main Methods:

• Synthesis of dinuclear Cu(I) and Ag(I) complexes using specific metal precursors and amidinate ligands.
• Reaction of synthesized complexes with carbon disulfide to induce insertion.
• Characterization of products using spectroscopic and analytical techniques.
• Luminescence spectroscopy to study photophysical properties and oxygen quenching.

Main Results:

• Dinuclear Cu(I) and Ag(I) complexes, Cu2[(2,6-Me2C6H3N)2C(H)]2 (1), Ag2[(2,6-Me2C6H3N)2C(H)]2 (2), Cu2[2,6-(i)Pr2C6H3N)2C(H)]2 (3), and Ag2[(2,6-(i)Pr2C6H3N)2C(H)]2 (4), were successfully synthesized.
• Carbon disulfide insertion into metal-nitrogen bonds of complex 1 yielded a tetranuclear Cu4S8 cluster (5).
• Complexes 3 and 4 reacted with CS2 to form hexanuclear clusters (7 and 8).
• Complexes 1 and 5 exhibited green luminescence, while complexes 2, 3, 4, 7, and 8 did not.
• Complexes 1 and 5 showed rapid and reversible luminescence quenching by oxygen.

Conclusions:

• Novel dinuclear copper and silver amidinate complexes were prepared.
• Carbon disulfide insertion leads to the formation of higher nuclearity clusters, showcasing unique reactivity.
• Complexes 1 and 5 possess luminescence properties that are efficiently quenched by oxygen, suggesting potential applications in sensing.