Crystalline, Porous Figure-Eight-Noded Covalent Organic Frameworks

Figure-eight macrocycles represent a fascinating class of π-conjugated units characterized by unique aesthetics and non-contact molecular crossing at the center. Despite progress in synthesis over the past century, research into inorganic, organic, and polymeric figure-eight materials remains in its infancy. Here we report the first examples of figure-eight covalent organic frameworks by condensing figure-eight knots to create extended porous figure-eight π architectures. A distinct feature is that polymerization interweaves figure-eight knots into double-decker layers, which upon supramolecular polymerization organize well-defined layer frameworks. The figure-eight frameworks exhibit a band gap of 2.3 eV and emit bright orange florescence with benchmark quantum yields. Remarkably, the donor-acceptor figure-eight skeletons convert the figure-eight knots into reduction centers and the linkers into oxidation sites upon light irradiation, enable charge transport and accumulation through π columns, while the built-in hydrophilic micropores allow rapid water and oxygen delivery via capillary effect. With these distinct features, the figure-eight frameworks function as a photocatalyst to produce hydrogen peroxide at high rate and efficiency with water/saltwater, oxygen/air, and light as sole inputs. This work paves a way to a new class of molecular frameworks, underpinning the study of well-defined figure-eight materials to explore unprecedented structures and functions so far we untouched.