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Hetero-Diels-Alder Reaction between Singlet Oxygen and Anthracene Drives Integrative Cage Self-Sorting
Yuchong Yang1, Tanya K Ronson1, Dingyu Hou2
1Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
Journal of the American Chemical Society
|August 23, 2023
Summary
Researchers explored dynamic metal-organic cages, forming different shapes like cubes and prisms from common building blocks. They discovered a way to selectively form a specific trigonal prismatic cage using light and guest molecules.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Dynamic combinatorial chemistry enables the formation of diverse molecular architectures from a common set of components.
- Self-sorting processes are crucial for selectively assembling complex supramolecular structures.
- Metal-organic cages offer tunable cavities for potential applications in host-guest chemistry.
Purpose of the Study:
- To investigate the formation and transformation of metal-organic cages from a common set of subcomponents.
- To explore the use of external stimuli, such as light and guest molecules, to control self-sorting and cage formation.
- To characterize the structures and guest-binding properties of the resulting metal-organic cages.
Main Methods:
- Equilibrium self-assembly of zinc(II) ions and organic ligands to form pseudocube, tetrahedron, and trigonal prism cages.
- Photoinduced hetero-Diels-Alder reaction with singlet oxygen to modify anthracene-containing ligands.
- Structural characterization using X-ray crystallography and analysis of guest binding properties.
Main Results:
- Three distinct zinc(II) cages (Zn8L6 pseudocube, Zn4L'4 tetrahedron, Zn6L3L'2 trigonal prism) were formed in equilibrium.
- Singlet oxygen transformed anthracene ligands to endoperoxides, driving selective formation of the Zn6L^O3L'2 trigonal prism.
- The trigonal prisms (Zn6L3L'2 and Zn6L^O3L'2) possess peanut-shaped cavities suitable for guest encapsulation.
- Guest binding also promoted the exclusive formation of the Zn6L3L'2 trigonal prism, demonstrating external control over self-sorting.
Conclusions:
- Integrative self-sorting can be controlled by chemical reactions (ligand modification) and external factors (guest binding).
- The trigonal prismatic cages exhibit unique internal structures and potential for selective guest encapsulation.
- Reversible transformations between cage assemblies can be achieved through stimuli-responsive reactions.
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