Compartmentalization of the aqueous space within a cell is necessary for life. In similar fashion to the nanometer-scale compartments in living systems, synthetic water-soluble coordination cages (WSCCs) can isolate guest molecules and host chemical transformations. Such cages thus show promise in biological, medical, environmental, and industrial domains. This review highlights examples of three-dimensional synthetic WSCCs, offering perspectives so as to enhance their design and applications. Strategies are presented that address key challenges for the preparation of coordination cages that are soluble and stable in water. The peculiarities of guest binding in aqueous media are examined, highlighting amplified binding in water, changing guest properties, and the recognition of specific molecular targets. The properties of WSCC hosts associated with biomedical applications, and their use as vessels to carry out chemical reactions in water, are also presented. These examples sketch a blueprint for the preparation of new metal–organic containers for use in aqueous solution, as well as guidelines for the engineering of new applications in water.

This review highlights transformation networks created with coordination cages. Such synthetic stimuli-controlled networks can help elucidate biological signal transduction, as well as enabling new functions and applications.

Selective anion extraction is useful for the recovery and purification of valuable chemicals, and in the removal of pollutants from the environment. Here we report that Fe^II₄L₄ cage 1 is able to extract an equimolar amount of ReO₄⁻, a high‐value anion and a nonradioactive surrogate of TcO₄⁻, from water into nitromethane. Importantly, the extraction was efficiently performed even in the presence of 10 other common anions in water, highlighting the high selectivity of 1 for ReO₄⁻. The extracted guest could be released into water as the cage disassembled in ethyl acetate, and then 1 could be recycled by switching the solvent to acetonitrile. The versatile solubility of the cage also enabled complete extraction of ReO₄⁻ (as the tetrabutylammonium salt) from an organic phase into water by using the sulfate salt of 1 as the extractant.

The reaction of sym-pentakis(4-aminothiophenyl)corannulene with 2-formyl-6-methyl-pyridine and Cu^I or 2-formyl-1,10-phenanthroline and M^II (Co or Zn) yields an S₁₀-symmetric five-fold interlocked [2]catenane of two interpenetrating [Cu^I₅L₂]⁵⁺ cages or D₅-symmetric [M^II₅L₂]¹⁰⁺ cages, respectively. The new structures were characterized by X-ray crystallography, NMR spectroscopy and mass spectrometry. Density functional theory computations point to dispersive energies on par with traditional covalent bond energies. Subcomponent exchange reactions favored formation of the [Co^II₅L₂]¹⁰⁺ cage over the [Cu^I₁₀L₄]¹⁰⁺ catenane. The single cage and catenane each co-crystalized with a guest corannulene to form a bowl-in-bowl sub-structure.