Crystalline Porphyrazine‐Linked Fused Aromatic Networks with High Proton Conductivity

Abstract Fused aromatic networks (FANs) have been studied in efforts to overcome the low physicochemical stability of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), while preserving crystallinity. Herein, we describe the synthesis of a highly stable and crystalline FAN (denoted as Pz‐FAN) using pyrazine‐based building blocks to form porphyrazine (Pz) linkages via an irreversible reaction. Unlike most COFs and FANs, which are synthesized from two different building blocks, the new Pz‐FAN is formed using a single building block by self‐cyclotetramerization. Controlled and optimized reaction conditions result in a highly crystalline Pz‐FAN with physicochemical stability. The newly prepared Pz‐FAN displayed a high magnitude (1.16×10 −2 S cm −1 ) of proton conductivity compared to other reported FANs and polymers. Finally, the Pz‐FAN‐based membrane was evaluated for a proton‐exchange membrane fuel cell (PEMFC), which showed maximum power and current densities of 192 mW cm −2 and 481 mA cm −2 , respectively.