Preparation of Versatile, Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

Abstract

Porous organic frameworks have shown a number of promising properties; however, their industrial application is usually hampered due to the lability of their linkages (imine, boroxine, etc.). Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulfide (PPS), we hypothesized that 2D and 3D poly-arylthioether frameworks would merge the attractive features common to porous frameworks and PPS in a single material. Herein, we report a Pd-catalysed C–S/C–S metathesis-based method to prepare new porous poly-arylthioether frameworks in good yields. The self-correcting nature of the process has enabled the synthesis of new, robust materials with high surface areas. Despite the frameworks’ extreme resistance to harsh chemicals, they can be fully recycled to recover the original building blocks using the same catalytic reaction. In addition, we demonstrate preliminary results showing that these materials have great potential in several environmentally relevant applications including metal capture, metal sensing and heterogeneous catalysis. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new materials.

Versatile Porous Poly(arylene ether)s via Pd-Catalyzed C–O Polycondensation

“…POPs with designed functional groups have emerged as a versatile platform for many potential applications, such as catalysis, sensing, and purification. 1,3,30,31 Our new bottom-up approach allows the installation of functionality using an elaborated monomer. Hence, we prepared aldehyde-containing PAE P17 (93% yield, M n = 11.8 kg/mol, Đ = 3.2) using the functionalized aryl dibromide monomer (Figure 2b).…”

Recent Metal-Catalyzed Methods for Thioether Synthesis

“…Moreover, it was demonstrated that thiophenols can also be used as electrophiles at 160 °C. A modified system was applied to the synthesis of porous poly(aryl thioether)s. 124…”