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

In recent years Pd(II) and Pt(II) cases have been reported wherein metals in square planar complexes were used as nucleophilic partners to construct supramolecular assemblies with electrophilic molecules like σ-hole and π-hole donors. The formation of such assemblies is based on the nucleophilicity and accessibility of the d orbital (in group-10 elements) in the square-planar complexes. This opens new avenues in inorganic chemistry and crystal engineering as it enriches the current toolbox of noncovalent interactions and supramolecular synthons thus allowing the design of new types of architectures in the solid state. This manuscript reports a comprehensive theoretical study characterizing π-hole⋯d[M] (M = group 10 element) interactions from an energetic point of view. Several computational tools based on the topology of the electron density are used. Examined systems had been identified by considering structures in the Cambridge Structural Database where this interaction was used to construct supramolecular assemblies. Several aromatic rings have been used, varying from π-basic to π-acid rings by adjusting the number of fluorine substituents. Moreover, the influence of metal⋯metal interactions on the nucleophilicity of the d orbital has been studied using MEP surface analysis. The π-hole energies are moderately strong (from -5 to -10 kcal mol) and the crucial role of dispersion forces is revealed.