Crystalline, Porous Helicene Covalent Organic Frameworks

Abstract Helicenes are a class of fascinating chiral helical molecules with rich chemistry developed continuously over the past 100 years. Their helical, conjugated, and twisted structures make them attractive for constructing molecular systems. However, studies over the past century are mainly focused on synthesizing helicenes with increased numbers of aromatic rings and complex heterostructures, while research on inorganic, organic, and polymeric helicene materials is still embryonic. Herein, we report the first examples of helicene covalent organic frameworks, i.e., [7]Helicene sp 2 c‐COF‐1, by condensing [7]Helicene dialdehyde with trimethyl triazine via the C=C bond formation reaction under solvothermal conditions. The resultant [7]Helicene sp 2 c‐COF‐1 exhibits prominent X‐ray diffraction peaks and assumes a highly ordered 2D lattice structure originated from the twisted configuration of [7]Helicene unit. The C=C linked [7]Helicene sp 2 c‐COF‐1 materials exhibited extended π conjugation and broadly tuned their absorption, emission, redox activity, photoconductivity, and light‐emitting activity, demonstrating rich multifunctionalities and great potentials in developing various applications. This work opens a way to a new family of COFs as well as helicene materials, enabling the exploration of unprecedented π architectures and properties.