Group-10 π-hole⋯d[M^II] interactions: a theoretical study of model systems inspired by CSD structures

Area of Science:

• Inorganic Chemistry
• Crystal Engineering
• Supramolecular Chemistry

Background:

• Square planar complexes of Pd(II) and Pt(II) can act as nucleophilic partners.
• This interaction is driven by the nucleophilicity and accessibility of the d-orbital in group-10 elements.
• This expands the toolbox for noncovalent interactions and supramolecular synthons.

Purpose of the Study:

• To conduct a comprehensive theoretical study of π-hole⋯d[MII] interactions.
• To characterize these interactions energetically.
• To explore their role in constructing solid-state architectures.

Main Methods:

• Utilized computational tools based on electron density topology.
• Analyzed structures from the Cambridge Structural Database.
• Employed MEP surface analysis to study metal⋯metal interactions.

Main Results:

• Characterized π-hole⋯d[MII] interactions energetically.
• Investigated systems with varying aromatic rings (π-basic to π-acid).
• Revealed the significant role of dispersion forces in these interactions.

Conclusions:

• π-hole⋯d[MII] interactions are moderately strong (-5 to -10 kcal mol-1).
• Dispersion forces play a crucial role in the formation of these supramolecular assemblies.
• This work provides insights into designing novel solid-state architectures.