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Coordination Sphere Hydrogen Bonding as a Structural Element in Metal-Organic Frameworks

Hawes, Chris S.



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.

Journal Article Type Article
Acceptance Date Apr 1, 2021
Online Publication Date Apr 1, 2021
Publication Date Apr 1, 2021
Journal Dalton Transactions
Print ISSN 1477-9226
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 50
Issue 18
Pages 6034-6049
Keywords Inorganic Chemistry
Publisher URL


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