Supramolecular Engineering of Crystalline Fullerene Micro‐/Nano‐Architectures

Abstract Fullerenes are a molecular form of carbon allotrope and bear certain solubility, which allow the supramolecular assembly of fullerene molecules—also together with other complementary compound classes—via solution‐based wet processes. By well‐programmed organizing these building blocks and precisely modulating over the assembly process, supramolecularly assembled fullerene micro‐/nano‐architectures (FMNAs) are obtained. These FMNAs exhibit remarkably enhanced functions as well as tunable morphologies and dimensions at different size scales, leading to their applications in diverse fields. In this review, both traditional and newly developed assembly strategies are reviewed, with an emphasis on the morphological evolution mechanism of FMNAs. The discussion is then focused on how to precisely regulate the dimensions and morphologies to generate functional FMNAs through solvent engineering, co‐crystallization, surfactant incorporation, or post‐fabrication treatment. In addition to C₆₀‐based FMNAs, this review particularly focuses on recently fabricated FMNAs comprising higher fullerenes (e.g., C₇₀) and metallofullerenes. Meanwhile, an overview of the property modulation is presented and multidisciplinary applications of FMNAs in various fields are summarized, including sensors, optoelectronics, biomedicines, and energy. At the end, the prospects for future research, application opportunities, and challenges associated with FMNAs are proposed.