Abstract
For nearly 15 years, the biological and biomedical applications of arene ruthenium metalla-assemblies have flourished. Today, the synthetic strategies to generate arene ruthenium assemblies are well-established, and these compounds offer tremendous possibilities in terms of structural diversities and chemical properties. However, the second coordination sphere is often poorly considered, if not ignored, when designing such arene ruthenium metalla-assemblies. These weak interactions (hydrogen bonding, hydrophobic, ionic, electrostatic, van der Waals, π-π stacking) that take place in the solid state or in solution are generally key interactions for the foreseen applications. Therefore, in this review, we want to emphasize this important property of arene ruthenium metalla-assemblies by showing examples dealing with second coordination sphere interactions and how this can be better integrated in the design of these versatile supramolecular metal-based entities.
Highlights
It is well-known that the second coordination sphere plays a major role in metal-based enzymatic transformations (Dudev et al, 2003)
We have been involved in the field of coordination-driven self-assembly, using piano-stool complexes as building blocks, and especially arene ruthenium complexes as biological agents (Therrien and Furrer, 2014; Therrien, 2015)
The introduction of functional groups that can generate weak interactions with biomolecules on either the arene, the building blocks or the guest molecules is essential for the development of biologically active arene ruthenium metalla-assemblies
Summary
It is well-known that the second coordination sphere (second shell) plays a major role in metal-based enzymatic transformations (Dudev et al, 2003) These additional interactions that take place in the proximity of the catalytic pocket can either stabilize the metal-substrate complex, stabilize the electronic state of the metal, orient the ligands to enhance the reactivity, act as proton and/or electron mediators, and so on (Ando et al, 1996; Botta, 2000; Steed, 2001; Haviv et al, 2018). The piano-stool unit provides three coordination sites at 90◦ from each other for a strategic
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