Computational insights into solvent encapsulation and host-guest recognition by calix[4]arene

Area of Science:

• Supramolecular Chemistry
• Computational Chemistry
• Materials Science

Background:

• Calix[4]arenes are versatile macrocyclic hosts with tunable properties.
• Understanding host-guest interactions is crucial for molecular recognition and materials design.
• Organic solvents play a vital role in chemical processes and material properties.

Purpose of the Study:

• To investigate the formation and stability of calix[4]arene/organic solvent inclusion complexes.
• To explore the influence of solvent guest molecules on calix[4]arene electronic properties.
• To elucidate the nature of non-covalent interactions within these complexes.

Main Methods:

• Computational modeling using the B3LYP-D3 functional and 6-311+G(d,p) basis set.
• Optimization of inclusion complexes in both gas and solvent phases.
• Analysis of interaction energies, thermodynamic parameters, frontier molecular orbitals, and non-covalent interactions.

Main Results:

• All investigated calix[4]arene/solvent complexes are energetically favorable.
• Calix[4]arene/dimethyl sulfoxide (CX[4]/DMSO) showed the highest gas-phase interaction energy (-76.57 kJ/mol).
• Complexation induced shifts in HOMO-LUMO densities, with energy gaps indicating kinetic stability.

Conclusions:

• Calix[4]arene inclusion complexes with organic solvents are thermodynamically stable.
• Non-covalent interactions and electrostatic potentials dictate the host-guest complexation behavior.
• Findings offer insights into host-guest chemistry and potential applications in molecular recognition.