Dynamic covalent bond from first principles: Diarylbibenzofuranone structural, electronic, and oxidation studies

Area of Science:

• Smart materials science
• Polymer chemistry
• Materials engineering

Background:

• Self-healing structures are a significant challenge in modern materials science.
• Dynamic covalent bonds offer a promising route to achieving self-healing properties.
• Diarylbibenzofuranone (DABBF) dynamic covalent bonds present an attractive solution.

Purpose of the Study:

• To investigate the reaction mechanism of diarylbibenzofuranone (DABBF) bond formation.
• To compare the DABBF bond formation with the competing autoxidation reaction.
• To understand the electronic and structural factors governing these reactions.

Main Methods:

• Density functional theory (DFT) calculations were employed.
• Total energy calculations were performed.
• Electronic and structural properties were analyzed.

Main Results:

• The formation of the DABBF bond was found to be barrierless.
• DABBF bond formation is kinetically favored over autoxidation.
• A charge transfer process leading to weakly bonded superoxide was identified as key.

Conclusions:

• The DABBF dynamic covalent bond is a superior pathway for self-healing applications compared to autoxidation.
• Understanding the reaction energetics is crucial for designing effective self-healing materials.
• This research provides fundamental insights into the chemistry of dynamic covalent bonds for smart materials.