Abstract
Self-assembly has emerged as a powerful approach to generating complex supramolecular architectures. Despite there being many crystalline frameworks reported in the solid state, the construction of highly soluble periodic supramolecular networks in a three-dimensional space is still a challenge. Here we demonstrate that the encapsulation motif, which involves the dimerization of two aromatic units within cucurbit[8]uril, can be used to direct the co-assembly of a tetratopic molecular block and cucurbit[8]uril into a periodic three-dimensional supramolecular organic framework in water. The periodicity of the supramolecular organic framework is supported by solution-phase small-angle X-ray-scattering and diffraction experiments. Upon evaporating the solvent, the periodicity of the framework is maintained in porous microcrystals. As a supramolecular ‘ion sponge’, the framework can absorb different kinds of anionic guests, including drugs, in both water and microcrystals, and drugs absorbed in microcrystals can be released to water with selectivity.
Highlights
Self-assembly has emerged as a powerful approach to generating complex supramolecular architectures
By utilizing coordination or hydrogen bonding as driving forces, a large number of supramolecular crystalline frameworks6, including a hydrogen bonding-stabilized supramolecular organic framework (SOF)7, have been constructed, many of which generate channels that allow for gas, solvent or guest absorption7–9
To the best of our knowledge, there are no prior examples of solutionphase 3D periodic supramolecular networks, a solutionphase two-dimensional (2D) periodic supramolecular framework had been created by us23
Summary
Self-assembly has emerged as a powerful approach to generating complex supramolecular architectures. By utilizing coordination or hydrogen bonding as driving forces, a large number of supramolecular crystalline frameworks, including a hydrogen bonding-stabilized supramolecular organic framework (SOF), have been constructed, many of which generate channels that allow for gas, solvent or guest absorption. By utilizing coordination or hydrogen bonding as driving forces, a large number of supramolecular crystalline frameworks, including a hydrogen bonding-stabilized supramolecular organic framework (SOF), have been constructed, many of which generate channels that allow for gas, solvent or guest absorption7–9 None of these crystalline frameworks can maintain their periodicity in solution. If selfassembly can be shown to drive the formation of periodic supramolecular networks in a 3D space in solution, rational design of molecular building blocks should lead to the construction of a variety of soluble ordered porous frameworks and offer new opportunities for the generation of advanced soft materials. We further demonstrate that the porous framework, as a family of 3D-ordered cationic supramolecular polyelectrolyte, can attract a variety of anionic organic molecules, including dyes, drugs, peptides, nucleic acids and poly(amidoamine) (PAMAM) dendrimers, in both solution and the solid state, and the attracted drugs can be released to water selectively in acidic medium
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