Radicalradical chalcogen bonds: CSD analysis and DFT calculations.

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Computational Chemistry

Background:

• Chalcogen bonding (ChB) is a significant non-covalent interaction.
• Radical systems present unique challenges and opportunities for ChB.
• Understanding ChB in radicals is crucial for designing novel materials.

Purpose of the Study:

• To investigate chalcogen bonding interactions involving radicals.
• To analyze the influence of substituents on ChB properties.
• To rationalize self-assembly motifs in the crystalline state.

Main Methods:

• Crystallographic analysis using the Cambridge Structural Database (CSD).
• Theoretical Density Functional Theory (DFT) calculations.
• Analysis of interaction energy, spin density, and charge/spin transfer.

Main Results:

• Benzodithiazolyl radical (BDTA) was used as a ChB acceptor.
• Dithiadiazolyl and diselenadiazolyl radicals served as ChB donors.
• Para-substituents (X) were found to affect interaction energy, spin density, and charge/spin transfer.

Conclusions:

• The study provides a detailed understanding of ChB in radical systems.
• Molecular surface electrostatic potentials accurately predict self-assembly motifs.
• Findings contribute to the rational design of crystalline materials through ChB.