Supramolecular organic frameworks (SOFs): homogeneous regular 2D and 3D pores in water

Abstract Studies on periodic porosity and related properties and functions have been limited to insoluble solid-state materials. Self-assembly provides a straightforward and efficient strategy for the construction of soluble periodic porous supramolecular organic frameworks (SOFs) in water from rationally designed molecular building blocks. From rigid tri- and tetra-armed building blocks and cucurbitu[8]ril (CB[8]), a number of two-dimensional (2D) honeycomb, square and rhombic SOFs can be generated, which is driven by CB[8]-encapsulation-enhanced dimerization of two aromatic units on the periphery of the multi-armed molecules. By utilizing the same three-component host−guest motif as the driving force, three-dimensional (3D) diamondoid and cubic SOFs can be obtained from tetrahedral and [Ru(bipy)3]2+-derived octahedral monomers and CB[8]. All of the 2D and 3D periodic frameworks are soluble in water, and are able to maintain the periodicity as well as the pore sizes in the solid state. 3D SOFs are highly efficient homogeneous polycationic frameworks for reversible adsorption of anionic species including organic dyes, peptides, nucleic acids, drugs, dendrimers and Wells-Dawson-typed polyoxametallates (WD-POMs). WD-POM molecules adsorbed in the [Ru(bipy)3]2+-based SOF can catalyse the reduction of proton to H2 upon visible-light sensitization of [Ru(bipy)3]2+, which allows multiple electron transfer from [Ru(bipy)3]2+ to WD-POM. This review summarizes the design, formation and characterization of this new family of self-assembled frameworks, highlights their applications as homogeneous porous materials and finally outlines some future research directions.