Diels-Alder Reaction Mechanisms of La@C₆₀ and Gd@C₆₀ Studied Using Density Functional Theory

Area of Science:

• Materials Science
• Computational Chemistry
• Organic Chemistry

Background:

• Encapsulating transition metals modifies fullerene electronic structure and reactivity.
• Fullerenes are key structures in materials science and nanotechnology.
• Diels-Alder reactions are fundamental in organic synthesis.

Purpose of the Study:

• Investigate Diels-Alder reaction mechanisms with endohedral fullerenes La@C60 and Gd@C60.
• Explore the impact of metal encapsulation on fullerene reactivity.
• Assess the influence of tricationic states and external electric fields.

Main Methods:

• Density Functional Theory (DFT) calculations.
• Investigated Diels-Alder reactions of cyclopentadiene with La@C60 and Gd@C60.
• Analyzed reaction mechanisms, energy barriers, and regioselectivity.

Main Results:

• Thermodynamically favorable encapsulation of La and Gd into C60 cages.
• La and Gd enhance Diels-Alder reactions, lowering activation barriers.
• Regioselectivity favoring 6-6 bonds in the fullerene remains unaffected.
• Considered the effect of external electric fields on the reactions.

Conclusions:

• Metal encapsulation in fullerenes favorably modulates reactivity for Diels-Alder reactions.
• Endohedral fullerenes La@C60 and Gd@C60 show enhanced reactivity.
• DFT provides insights into tuning fullerene properties for advanced applications.