Thallophilic Tl(i)-Tl(i) contacts mediated by Tl-aryl interactions. A computational study

Area of Science:

• Computational Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Thallium complexes can exhibit unusual bonding interactions.
• Understanding metallophilic interactions is key to designing novel materials.

Purpose of the Study:

• To computationally investigate the dimerization of a thallium-β-triketimine complex.
• To elucidate the role of counter ions in mediating thallium-thallium interactions.

Main Methods:

• Density Functional Theory (DFT) calculations.
• Single point energy calculations using crystallographic structures.
• Energy Decomposition Analysis (EDA).

Main Results:

• The thallium complex forms dimers with close Tl-Tl contacts.
• The system is bound only when BArF counter ions are included.
• Electrostatic interactions are repulsive without counter ions but attractive with them.
• Metallophilic interaction is mediated by counter ions, even diffuse ones.

Conclusions:

• Counter ions play a critical role in stabilizing thallium dimers.
• Favorable electrostatics from anions are necessary for Tl-Tl bonding.
• This finding has implications for the design of thallium-based materials.