Using nature's blueprint porous organic polymeric nanotraps enables the interfacial activation of the hosted amine and CO2

Abstract

Porous organic polymers (POPs) constructed via Schiff-base chemistry has garnered increasing attention as advanced materials for heterogeneous catalysis, owing to their inherent structural tunability, high surface area, and chemical stability. Herein, we report the rational design and synthesis of a histidine-functionalized porous organic polymer, namely His-POP, formed via a one-pot Schiff-base condensation method, followed by post-synthetic metalation with ZnCl₂ to afford a zinc-coordinated framework, Zn@His-POP. The metalated polymer was employed as an efficient and recyclable catalyst for the N-formylation of amines using phenylsilane as a mild hydride donor, which exhibited excellent catalytic activity across a broad range of substrates under mild conditions. The enhanced catalytic performance is attributed to the cooperative effect between the Zn(II) centres and the histidine-functionalized microporous environment, which facilitates substrate activation and product release. XAS analysis provided important insight into the local coordination environment of Zn species within the polymeric framework, supporting the formation of Zn–N/O coordination sites without the presence of Zn aggregates. Furthermore, DFT studies offered a mechanistic understanding of CO₂ activation and elucidated the role of Zn-centered active sites in facilitating the N-formylation pathway. This work underscores the potential of bioinspired, metal-functionalized POPs as robust platforms for sustainable catalysis and paves the way for the development of next-generation nanozyme-mimetic materials.