Skeletal Editing by Tip-Induced Chemistry.

Area of Science:

• Chemistry
• Materials Science
• Nanotechnology

Background:

• Skeletal editing of cyclic molecules is crucial for drug discovery and green chemistry.
• Previous methods were limited to solution-phase synthesis.

Purpose of the Study:

• To extend skeletal editing to the single-molecule scale.
• To demonstrate tip-induced chemical transformations on individual molecules.

Main Methods:

• Utilized scanning probe microscopy (atomic force microscopy and scanning tunneling microscopy) for atomic-scale manipulation and characterization.
• Performed tip-induced oxygen deletion and ring contraction reactions on an oxygen-containing seven-membered ring adsorbed on bilayer NaCl films.
• Employed density functional theory (DFT) calculations to elucidate reaction mechanisms.

Main Results:

• Successfully demonstrated single-molecule skeletal editing via tip-induced reactions.
• Generated molecules containing the perylene skeleton from the starting cyclic precursor.
• Characterized reaction products at the atomic scale, confirming the structural transformations.
• Gained mechanistic insights into the tip-induced chemical processes.

Conclusions:

• Tip-induced chemistry can be effectively applied for single-molecule synthesis.
• This work expands the capabilities of scanning probe microscopy for chemical transformations.
• The developed methodology offers new possibilities for constructing complex molecular architectures at the single-molecule level.