Halogen Bond-Involving Self-Assembly of Iodonium Carboxylates: Adding a Dimension to Supramolecular Architecture

Abstract

We designed 0D, 1D, and 2D supramolecular assemblies made of diaryliodonium salts (functioning as double σ-hole donors) and carboxylates (as σ-hole acceptors). The association was based on two charge-supported halogen bonds (XB), which occurred between IIII sites of the iodonium cations and the carboxylate anions. The sequential introduction of the carboxylic groups in the aryl ring of the benzoic acid added a dimension to the 0D supramolecular organization of the benzoate, which furnished 1D-chained and 2D-layered structures when terephthalate and trimesate anions, correspondingly, were applied as XB acceptors. The structure-directing XB were studied using DFT calculations under periodic boundary conditions and were followed by the one-electron-potential analysis and the Bader atoms-in-molecules topological analysis of electron density. These theoretical methods confirmed the existence of the XB and verified the philicities of the interaction partners in the designed solid-state structures.

Intermolecular Metal-Involving Pnictogen Bonding: The Case of σ-(SbIII)-Hole···dz2[PtII] Interaction

“…The one-electron potential (OEP) , was successfully used ,− for the visualization of shared- and lone electron pairs as they explicitly demonstrate negative OEP values in the corresponding areas. OEP is defined as ∇ 2 ρ/4ρ – |∇ρ| 2 /8ρ 2 and therefore does not depend on the wave function, and it is applicable for pseudopotential calculations, where the wave function is not calculated for core electrons.…”

“…Crystal ,− ,− and cluster , calculations, performed in the framework of these methodologies, have been successfully used for studies of noncovalent interactions in the solid state. We have also compared the senarmontite Sb 4 O 6 experimental charge density with the electron density calculated for the structure by these methodologies (Section S5 in the SI), and both crystal and cluster models showed good agreement in BCP parameters for O–Sb···O PnBs.…”