The Nature of Intermolecular CuI⋅⋅⋅CuIInteractions: A Combined Theoretical and Structural Database Analysis

Abstract

The nature of intermolecular interactions between dicoordinate Cu^I ions is analyzed by means of combined theoretical and structural database studies. Energetically stable Cu^I⋅⋅⋅Cu^I interactions are only found when the two monomers involved in the interaction are neutral or carry opposite charges, thus allowing us to speak of bonding between the components of the bimolecular aggregate. A perturbative evaluation of the components of the intermolecular interaction energies, by means the IMPT scheme of Stone, indicates that both the Coulombic and dispersion forces are important in determining the Cu^I⋅⋅⋅Cu^I bonding interactions, because only a small part of that energy is attributable to Cu⋅⋅⋅Cu interactions, while a large component results from Cu⋅⋅⋅ligand interactions. The electrostatic component is the dominant one by far in the interaction between charged monomers, while in the interaction between neutral complexes, the electrostatic component is found to be of the same order of magnitude as the dispersion term. Bimolecular aggregates that have like charges are repulsive by themselves, and their presence in the solid state results from anion⋅⋅⋅cation interactions with ions external to this aggregate. In these cases, the short-contact Cu⋅⋅⋅Cu interactions here should be more properly called counterion-mediated Cu⋅⋅⋅Cu bonds.