Changing weak halogen bonds into strong ones through cooperativity with beryllium bonds

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Supramolecular Chemistry

Background:

• Beryllium bonds and halogen bonds are crucial non-covalent interactions.
• Understanding their interplay is key to designing novel molecular systems.

Purpose of the Study:

• To investigate the mutual interactions between beryllium and halogen bonds.
• To quantify the cooperative effects in H2Be···FCl···Base complexes.
• To correlate cooperativity with Lewis base properties.

Main Methods:

• Density functional theory (DFT) calculations using M06-2X/6-31+G(d,p).
• Validation against ab initio coupled cluster (CCSD/aug-cc-pVTZ) calculations.
• Atoms in Molecules (AIM) theory for electron density topology and atomic energy analysis.

Main Results:

• Strong cooperative effects exist between beryllium and halogen bonds.
• Decomposition of stabilization energy reliably quantifies halogen bond interactions.
• Cooperativity intensifies with increasing Lewis base strength.

Conclusions:

• Beryllium and halogen bonds exhibit significant mutual interaction and cooperativity.
• AIM theory effectively characterizes these interactions.
• Lewis base basicity is a key factor modulating cooperative effects.