Three-dimensional van der Waals Open Frameworks

Open framework materials are constructed by connecting molecular components via strong bonds. Here, we show van der Waals interaction, which has been believed to be too weak for the framework construction, joints molecular building blocks into a series of robust three-dimensional frameworks, so-called van der Waals frameworks (WaaFs). The success relies on the use of metal-organic polyhedra (MOPs) with a size over 2 nm as building blocks. The well-defined faces composed of large aromatic molecules increase the intermolecular contact area to gain interaction energy over 400 kJ/mol. The octahedral shape of MOPs directs their packing into a diamond network with large extrinsic porosity. We confirm that one of the WaaFs shows over 2,000 m2 g-1 specific surface area.