Exploiting Reusable Edge‐Functionalized Metal‐Free Polyphthalocyanine Networks for Efficient Polymer Synthesis at Near Infrared Wavelengths

Heterogeneous catalysts are highly advantageous for industrial applications owing to their distinctive merits including easy separation and effective recovery. However, utilizing heterogeneous photocatalysts to harness longer wavelength light remains a critical area of research. This contribution explores the use of edge-functionalized metal-free polyphthalocyanine networks (PPc-x) to promote efficient polymer synthesis under near infrared (NIR) light irradiation. Our screening process revealed that both phenyl-edged PPc-x (PPc-p) and naphthyl-edged PPc-x (PPc-n) offer promising performance for photopolymerization. With the assistance of ppm-level PPc-n catalyst, well-defined polymers were synthesized within a few hours under the regulation of three NIR lights, regardless of shielded by synthetic and biological barriers. An excellent control over the molecular weight and molecular weight distribution was achieved. Furthermore, PPc-x can be easily recovered and reused for multiple cycles, with negligible leaching and maintenance of the catalytic performance. This study expands a new avenue in developing versatile photocatalysts for the modern synthetic toolkits and offer benefits in diverse applications.