Theoretical insights into intermolecular interactions during d⁸ organometallic self-aggregation

Area of Science:

• Inorganic Chemistry
• Supramolecular Chemistry
• Computational Chemistry

Background:

• Metallophilicity was historically viewed as the primary driver for aggregation in metal-organic complexes.
• However, other intermolecular forces also significantly influence complex aggregation.

Purpose of the Study:

• To theoretically investigate intermolecular interactions in the aggregation of planar organoplatinum(II) complexes.
• To elucidate the roles of Pt-Pt interactions, dispersion, and electrostatics in aggregate formation.

Main Methods:

• Theoretical study of platinum(II) complex monomers and oligomers.
• Analysis of structures, thermodynamic properties, and electronic structures.
• Investigation of intermolecular interaction contributions.

Main Results:

• Dispersion interactions were identified as the strongest attractive forces between Pt-complexes.
• Metal-metal (Pt-Pt) interactions were found to be less dominant than ligand interactions but significantly affected frontier molecular orbitals.
• Thermodynamically stable aggregates with higher interaction energies were preferentially formed.
• Aggregates with greater electrostatic attraction and lower dipole moments were favored during aggregation.

Conclusions:

• Intermolecular forces beyond metallophilicity, particularly dispersion and electrostatics, are crucial for platinum(II) complex aggregation.
• Aggregate stability is linked to interaction energy, electrostatic attraction, and dipole moment characteristics.
• Understanding these interactions is key to designing and controlling the assembly of organometallic complexes.