Literature on the Synthesis of Modulator‐Assisted Covalent–Organic Frameworks (MA‐COFs): A Review

Abstract Covalent–organic frameworks (COFs) owe their remarkable efficiency and versatility to an array of superior structural attributes, including crystallinity, surface area, crystal size, pore distribution, and stability. Although myriad methods have sought to enhance these traits, a singular breakthrough emerged from our research: the strategic use of a lone modulator that elevates all these properties, yielding high‐quality Modulator‐Assisted COFs (MA‐COFs). By deftly slowing monomer incorporation during synthesis, modulators orchestrate the creation of exquisitely ordered crystalline structures, amplify surface area, and foster larger, more resilient crystal domains. Beyond this, they refine pore distribution and fortify stability, unveiling a suite of extraordinary physical and chemical properties. The careful selection and optimization of modulators prove pivotal, directly shaping COF performance and integrity. This review meticulously explores the transformative influence of modulators in COF synthesis, shedding light on mechanisms that drive structural advancements and pinpointing critical efficacy factors. Such strategic deployment not only revolutionizes COF synthesis but also magnifies its potential across diverse scientific and industrial realms. Ultimately, these insights affirm modulators as essential instruments for sculpting COFs of unmatched performance and durability, charting new paths in catalysis and energy storage.