Structural Insights into AgBi(SC₁₂H₂₅)₄ Mixed-Metal n-Alkanethiolate: Heterometallic Thiolate Bridging and...

Area of Science:

• Materials Science
• Inorganic Chemistry
• Solid-State Chemistry

Background:

• Long-chain metal thiolates (MTs) are established inorganic-organic hybrid materials with a metal-sulfur core and hydrocarbon chains.
• While MT structures are well-understood, mixed-metal thiolates (MMTs) with heterometals remain largely unexplored structurally.
• Existing MMT research is limited, leaving their structural characteristics and self-assembly mechanisms unknown.

Purpose of the Study:

• To synthesize and elucidate the crystal structure of a novel mixed-metal thiolate (MMT).
• To investigate the heterometal arrangement and intermolecular interactions within the MMT.
• To understand the relationship between structure, self-assembly, and electronic properties in MMTs.

Main Methods:

• Synthesis of the mixed-metal thiolate AgBi(SC12H25)4.
• Structural elucidation using X-ray absorption fine structure (XAFS) spectroscopy.
• Computational analysis employing density functional theory (DFT) calculations.

Main Results:

• The AgBi MMT forms discrete molecular units [RS-Ag-SR-Bi(SR)2] with intramolecular Ag-Bi μ2-thiolate bridges.
• Strong intermolecular Ag···Bi metallophilic interactions (2.72 Å) drive self-assembly.
• Intermolecular metal-to-metal charge transfer, facilitated by thiolate bridges, explains UV-Vis absorption maxima.

Conclusions:

• The study provides the first structural insights into MMTs, revealing unique heterometal arrangements.
• Short Ag···Bi distances and thiolate-mediated interactions are key to MMT self-assembly and properties.
• This work lays the foundation for designing novel MMTs with tailored electronic and optical characteristics.