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Bidirectional Suzuki Catalyst Transfer Polymerization of Poly(p‑phenylene)
Christina M Dadich1,2, Felix R Fischer1,2,3,4
1Department of Chemistry, University of California, Berkeley, California 94720, United States.
Macromolecules
|March 2, 2026
Summary
A new bidirectional Suzuki catalyst transfer polymerization (SCTP) system using dinuclear palladium initiators enables precise control over polymer functionalization. This method allows for tailored synthetic handles at the polymer core and chain ends for advanced applications.
Area of Science:
- Polymer Chemistry
- Organic Electronics
- Materials Science
Background:
- Suzuki catalyst transfer polymerization (SCTP) is effective for length-controlled poly-(p-phenylene) synthesis.
- Regio-controlled functionalization of polymer backbones and chain ends is crucial for organic semiconductor integration but remains challenging.
Purpose of the Study:
- To develop a bidirectional SCTP system for precise polymer functionalization.
- To enable late-stage regio-controlled and chemoselective derivatizations of polymers.
Main Methods:
- Utilized a bidirectional SCTP system with dinuclear palladium-(II) initiators.
- Employed functional groups transferred during initiation and termination steps.
- Characterized polymer properties using size exclusion chromatography (SEC) and NMR spectroscopy.
Main Results:
- Demonstrated independent control over synthetic handles at the polymer core and chain ends.
- Achieved precise control over molecular weight (Mn), dispersity (Đ), and degree of polymerization (DP).
- Showcased functional group interconversion and high termination efficiency.
Conclusions:
- The bidirectional SCTP system offers a flexible toolbox for late-stage polymer conjugation.
- Enables chemoselective anchoring for integration with functional electronics.
- Facilitates bioorthogonal conjugation for molecular sensing applications.
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