Mechanochemical Diels-Alder Reactions: Conceptual Density Functional Theory and Information-Theoretic Analyses

Area of Science:

• Green Chemistry
• Computational Chemistry
• Organic Synthesis

Background:

• Mechanochemistry enables environmentally friendly synthesis of organic compounds.
• Retro Diels-Alder reactions are explored under mechanochemical conditions.
• Computational tools are essential for understanding reaction mechanisms.

Purpose of the Study:

• To investigate seven retro Diels-Alder reactions using mechanochemical methods.
• To apply Conceptual Density Functional Theory (CDFT) to analyze force-dependent properties.
• To determine the influence of external force on chemical reactivity and stability.

Main Methods:

• Utilized Constrained Geometries Simulate External Force (CoGEF) for Morse potential and bond rupture force calculations.
• Employed Conceptual Density Functional Theory (CDFT) for global and local descriptor analysis.
• Calculated force-dependent responses of ionization energy, electron affinity, hardness, electrophilicity, Fukui functions, and information-theoretic descriptors.

Main Results:

• The force-dependent response of ionization energy, electron affinity, electronegativity, hardness, and electrophilicity was found to be negative.
• Local descriptors including Fukui functions and philicity were determined.
• Force-dependent responses of information-theoretic descriptors and energy terms were calculated.

Conclusions:

• Mechanochemical analysis provides a deeper understanding of bond rupture and reactivity under force.
• CDFT effectively describes chemical concepts in response to external mechanical forces.
• This work contributes to the development of green synthesis strategies through mechanochemistry.