Vertical Step-Growth Polymerization Driven by Electrochemical Stimuli from an Electrode

Area of Science:

• Electrochemistry
• Polymer Chemistry
• Materials Science

Background:

• Electropolymerization is crucial for creating functional materials.
• Controlled synthesis of molecular architectures remains a challenge.
• Surface-confined molecular wires offer potential for advanced catalysis.

Purpose of the Study:

• To present a novel vertical step-growth polymerization method.
• To synthesize sequence- and topology-controlled molecular wires.
• To investigate the electrocatalytic performance of these molecular wires for water oxidation.

Main Methods:

• Vertical step-growth polymerization using electrochemical switching.
• Dimerization of RuII(bda)AB monomers via A-A or B-B coupling.
• Fabrication of self-assembled monolayers and molecular wires on ITO glass.

Main Results:

• Achieved sequence- and topology-controlled synthesis of surface-confined molecular wires with single-molecule precision.
• Demonstrated electrochemical dimerization at oxidative and reductive potentials.
• Observed increased electrocatalytic activity for water oxidation with increasing molecular wire length.

Conclusions:

• The developed electrochemical polymerization enables precise control over molecular wire synthesis.
• Vertically oriented molecular wires exhibit superior electrocatalytic performance for water oxidation.
• This method provides a new platform for designing advanced molecular electronic devices.