Tailoring polymer-metal-organic frameworks (polyMOFs) using telechelic poly(octenamer)s.

Area of Science:

• Materials Science
• Polymer Chemistry
• Nanotechnology

Background:

• Polymer-metal-organic frameworks (polyMOFs) are hybrid materials with potential applications, but their design is limited by polymer building block synthesis.
• Previous polyMOF designs using random copolymers achieved low loading (30%) of benzene-1,4-dicarboxylic acid (H2bdc) monomers.

Purpose of the Study:

• To overcome limitations in polyMOF design by developing a new method for high monomer incorporation.
• To synthesize and characterize novel polyMOFs with tunable properties using tailored polymer ligands.

Main Methods:

• Synthesized H2bdc-tagged cyclooctene derivatives and homopolymerized them via controlled olefin-metathesis polymerization.
• Utilized a novel chain-transfer agent (CTA) to create RAFT telechelic homopolymers.
• Produced ABA-type triblock copolymers by using the homopolymer as a macroinitiator for styrene polymerization.
• Fabricated polyMOFs by combining the synthesized polymers with Zn(ii).

Main Results:

• Achieved 100% incorporation of H2bdc-containing monomers into poly(octenamer) ligands.
• Successfully synthesized ABA triblock copolymers with a central poly(octenamer) block and terminal polystyrene (PS) blocks.
• Created polyMOFs with tunable morphologies controlled by polymer architecture and composition.
• Observed reversible glassy-to-rubbery transitions in crystalline polyMOFs at elevated temperatures (>100 °C) due to thermoplastic PS domains.

Conclusions:

• The study presents a novel and efficient method for synthesizing polyMOFs with high monomer loading.
• The developed polyMOFs demonstrate tunable structural characteristics and unique thermomechanical properties.
• This approach advances the design and application of polymer-metal-organic frameworks.