Coordination sphere hydrogen bonding as a structural element in metal-organic Frameworks

In the design of new metal-organic frameworks, the constant challenges of framework stability and structural predictability continue to influence ligand choice in favour of well-studied dicarboxylates and similar ligands. However, a small subset of known MOF ligands contains suitable functionality for coordination sphere hydrogen bonding which can provide new opportunities in ligand design. Such interactions may serve to support and rigidity the coordination geometry of mononuclear coordination spheres, as well as providing extra thermodynamic and kinetic stabilisation to meet the challenge of hydrolytic stability in these materials. In this perspective, a collection of pyrazole, amine, amide and carboxylic acid containing species are examined through the lens of (primarily) inner-sphere hydrogen bonding. The influence of these interactions is then related to the overall structure, stability and function of these materials, to provide starting points for harnessing these interactions in future materials design.