A μ9-iodide in a tricapped trigonal-prismatic geometry

Area of Science:

• Inorganic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Silver complexes are known for their diverse structures and luminescent properties.
• The exploration of polynuclear metal clusters continues to reveal novel bonding motifs and properties.
• Iodine's role in bridging metal centers in clusters is an area of ongoing investigation.

Purpose of the Study:

• To synthesize and characterize novel undecanuclear silver complexes.
• To investigate the structural implications of a central μ(9)-iodine atom within a silver cluster.
• To explore the luminescent properties of these newly synthesized silver-iodine complexes.

Main Methods:

• Single-crystal X-ray diffraction for structural determination.
• Luminescence spectroscopy for photophysical property analysis.
• Elemental analysis and spectroscopic techniques (NMR, IR) for characterization.

Main Results:

• Successful synthesis of two luminescent undecanuclear silver complexes, [Ag(11)(μ(9)-I)(μ(3)-I)(3){E(2)P(O(i)Pr)(2)}(6)](PF(6)) (E = S, Se).
• The complexes feature a central μ(9)-iodine atom encapsulated within a pentacapped trigonal-prismatic silver skeleton.
• Characterization confirmed the unique structural motif and the presence of luminescent behavior in both yellow (S) and orange (Se) complexes.

Conclusions:

• The reported silver complexes represent the first instance of a μ(9)-iodine atom stabilizing such a complex silver cluster.
• The pentacapped trigonal-prismatic silver framework provides a unique environment for the central iodine.
• These findings expand the understanding of metal-iodine cluster chemistry and offer potential for new luminescent materials.