(Bio)Functionalisation of Metal-Organic Polyhedra by Using Click Chemistry.

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Organic Chemistry

Background:

• The surface chemistry of Metal-Organic Polyhedra (MOPs) dictates their interactions with external substances, influencing their physicochemical properties.
• Tailoring MOP surface functionality is key to expanding their applications in areas like catalysis, sensing, and drug delivery.

Purpose of the Study:

• To develop a post-synthetic modification strategy for MOPs using click chemistry.
• To demonstrate the efficient and diverse functionalization of MOP surfaces with various chemical moieties.

Main Methods:

• Synthesis of a novel Rh(II)-based MOP featuring 24 surface alkyne groups.
• Post-synthetic modification of the MOP using copper(I)-catalysed, azide-alkyne cycloaddition (CuAAC) click reactions.
• Characterization of functionalized MOPs to confirm successful modification and retention of functional group properties.

Main Results:

• A novel Rh(II)-based MOP with 24 accessible surface alkyne groups was successfully synthesized.
• CuAAC click reactions enabled dense functionalization of the MOP surface with polymers, carboxylic acids, phosphonic acids, and biotin at room temperature.
• The integrity of the MOP structure was maintained throughout the functionalization process.
• Anchored biotin moieties retained their specific recognition capabilities.

Conclusions:

• CuAAC click chemistry provides a versatile and efficient platform for the post-synthetic functionalization of MOPs.
• This approach significantly broadens the scope of MOP applications by enabling precise control over surface properties.
• The ability to introduce diverse functionalities, including biomolecules, opens new avenues for MOPs in advanced material design.