Intercage Polymerization of Postfunctionalized Phosphine Organic Prisms into Cage-Based Assemblies with Tunable...

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Nanotechnology

Background:

• Extensive research has focused on designing porous organic cages (POCs) with specific geometries and topologies.
• However, utilizing these pre-formed cages as building blocks for infinite, cage-based superstructures remains a significant challenge.

Purpose of the Study:

• To develop a method for constructing infinite cage-based supramolecular polymers and hierarchical superstructures.
• To explore the self-assembly behavior of vertex-modified phosphine organic prisms as ditopic cage monomers.

Main Methods:

• Design and synthesis of vertex-modified phosphine organic prisms via postfunctionalization.
• Achieving intercage supramolecular polymerization through metal coordination and π-π dimerization.
• Hierarchical self-assembly of cage-polymers into diverse morphologies (fibers, lamellae, vesicles) controlled by cosolvents.

Main Results:

• Successful creation of cage-by-cage polymers from ditopic cage monomers.
• Demonstration of hierarchical organization into 1D, 2D, and 3D superstructures.
• Evidence of cosolvent-controlled regulation of structural hierarchies and self-assembled shapes.

Conclusions:

• This work presents a viable strategy for building infinite cage-based supramolecular assemblies.
• The developed approach paves the way for the creation of novel cage-based nanomaterials with tunable structures.
• The findings open new avenues in supramolecular chemistry and materials science for designing complex architectures.