Polymerization Order in the Synthesis of 2D Block Supramolecular Copolymers

Area of Science:

• Polymer Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Monomer order is crucial in living polymerization for block copolymers.
• The impact of monomer sequence on 2D supramolecular block copolymerization is unexplored.
• Porphyrin-based monomers are utilized for constructing 2D supramolecular polymers.

Purpose of the Study:

• Investigate the effect of monomer addition order on 2D seeded/living supramolecular block copolymerization.
• Understand how monomer sequence influences growth modes and resulting nanostructure.
• Determine the role of secondary nucleation in 2D supramolecular polymer formation.

Main Methods:

• Utilized porphyrin-based monomers for supramolecular polymerization.
• Employed a 2D seeded/living approach for block copolymer synthesis.
• Analyzed distinct growth modes resulting from inverted monomer addition sequences.

Main Results:

• Inverting the order of monomer polymerization leads to different growth modes in 2D supramolecular block copolymers.
• Secondary nucleation was identified as a key process in one of the observed growth modes.
• Secondary nucleation occurring before 2D growth results in nanosheets with uncontrolled areas and rough edges.

Conclusions:

• The sequence of monomer addition significantly affects the morphology and growth of 2D supramolecular polymers.
• Understanding secondary nucleation is vital for controlling the formation of well-defined 2D supramolecular structures.
• This study provides insights into the directed self-assembly of complex 2D materials.