This Account describes our efforts over the last decade to synthesize self-assembled metal–ligand cage complexes that display reactive functional groups on their interiors. This journey has taken us down a variety of research avenues, including studying the mechanism of reversible self-assembly, analyzing ligand self-sorting properties, post-assembly reactivity, molecular recognition, and binding studies, and finally reactivity and catalysis. Each of these individual topics are discussed here, as are the lessons learned along the way and the future research outlook. These self-assembled hosts are the closest mimics of enzymes to date, as they are capable of size- and shape-selective molecular recognition, substrate activation and turnover, as well as showing less common ‘biomimetic’ properties such as the ability to employ cofactors in reactivity, and alter the prevailing mechanism of the catalyzed reactions. 1 Introduction 2 Paddlewheels and Self-Sorting Behavior 3 First-Row Transition-Metal-Mediated Assembly: Sorting and Stereochemical Control 4 Post-Assembly Reactivity 5 Molecular Recognition and Catalysis 6 Conclusions and Outlook
Controlled self-sorting in self-assembled cage complexes
In this frontier article we highlight recent advances in subcomponent self-sorting in self-assembled metal–ligand cage complexes, with a focus on selective discrimination between ligands that contain highly similar metal-coordinating groups. Effects such as varying ligand length, coordination angle and backbone flexibility, as well as the introduction of secondary weak forces such as hydrogen bonds can be exploited to favor either narcissistic or social self-sorting. We highlight these creative solutions, and emphasize the challenges that remain in the development of functional self-assembled heterocomplexes.
- Award ID(s):
- 1708019
- Publication Date:
- NSF-PAR ID:
- 10067374
- Journal Name:
- Dalton Transactions
- Volume:
- 46
- Issue:
- 43
- Page Range or eLocation-ID:
- 14719 to 14723
- ISSN:
- 1477-9226
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Publisher's Version of Record
- https://doi.org/10.1039/c7dt03399k
