Abstract
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.
Highlights
This section touches upon key advances in metallosupramolecular chemistry, which have led to the emergence and development of water-soluble coordination cages (WSCCs) (Figure 1), with an emphasis on the synthetic strategies that allow solubility and stability in water
This review has attempted to span the scope of threedimensional water-soluble metal−organic cages and summarize the strategies required to render them soluble and stable in aqueous media, where they may find their widest scope of application
Chemists have begun to endow such cages with photoactive and luminescent features, chiral attributes, and the capacity for highly selective recognition. These attributes enable the solubilization of hydrophobic molecules in water, the safeguarding of reactive guests, encapsulation of highly solvated molecules, the transport of chemicals into cells, and the realization of chemical transformations with improved rates or unexpected product distributions
Summary
This review will explore synthetic methods for the construction of water-soluble metal−organic cages and the aqueous applications of these cages. These aspects will be discussed in the context of the peculiarities of supramolecular chemistry in water,[20,21] where the hydrophobic effect is a key protagonist.[22−25] The cages in question are molecular architectures enclosing three-dimensional cavities, assembled via multiple donor→metal coordination bonds. The review is divided into sections covering the synthesis of WSCCs, and their applications to binding guests and carrying out chemical reactions. Beyond WSCCs, we anticipate that these design principles may be extended to other metallosupramolecular systems and stimulate further design of new aqueous metallacycles, self-healing coordination polymers, rotaxanes and catenanes
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