Radical-Induced Hierarchical Self-Assembly Involving Supramolecular Coordination Complexes in Both Solution and Solid...

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Organic Chemistry

Background:

• Hierarchical self-assembly (HSA) is crucial in supramolecular chemistry.
• Exploring new supramolecular interactions is vital for advancing HSA.
• Triphenylamine (TPA) moieties offer unique electronic properties for molecular design.

Purpose of the Study:

• To investigate a novel radical-induced HSA process.
• To utilize light-triggered radical generation for driving self-assembly.
• To explore the fundamental TPA radical interaction in metallacycles.

Main Methods:

• Synthesis of rhomboidal metallacycles containing TPA moieties.
• Light-induced radical generation and characterization.
• Transmission Electron Microscopy (TEM) and HAADF-STEM imaging.
• Coarse-grained molecular dynamics simulations.

Main Results:

• Demonstrated light-induced radical generation from TPA-based metallacycles.
• Observed hierarchical self-assembly into nanovesicles and nanospheres.
• Elucidated the HSA mechanism involving TPA radical and metallacycle stacking interactions.
• Confirmed increased stability of TPA radical cations during self-assembly.

Conclusions:

• Established a new radical-induced HSA pathway for supramolecular coordination complexes (SCCs).
• Provided fundamental insights into TPA radical interactions.
• Opened avenues for developing stable organic radical cations.