Exploring Cation-π Interaction in the Complexes with B≡B Triple Bond: A DFT Study

Area of Science:

• Computational chemistry
• Quantum chemistry
• Materials science

Background:

• Metal ion-π interactions are crucial in various chemical systems.
• Diboryne (B≡B) presents a unique electronic structure for such interactions.

Purpose of the Study:

• To investigate metal ion-π interactions with diboryne.
• To compare the stability of cation-π complexes and sandwich structures.

Main Methods:

• Density functional theory (DFT) calculations were employed.
• Interaction energies and global hardness were computed.
• Koopmans' theorem and the ΔSCF method were utilized.

Main Results:

• Larger metal ions (Na+, Mg2+, Ca2+, Al3+) form cation-π complexes with diboryne.
• Interaction strength decreases with increasing metal ion size (for same charge).
• Higher cation charge leads to stronger B≡B triple bond interactions.
• Sandwich complexes are more stable than cation-π complexes.
• Global hardness values corroborate interaction energy trends.
• Most complexes show stability in polar solvents.

Conclusions:

• Metal ion-π interactions with diboryne are influenced by ion size and charge.
• Diboryne-based sandwich structures offer enhanced stability.
• The findings provide insights into the behavior of diboryne in different chemical environments.