We derive design principles for the assembly of rectangular tetramines into Zn8L6 pseudo-cubic coordination cages. Because of the rectangular, as opposed to square, geometry of the ligand panels, and the possibility of either Delta or ? handedness of each metal center at the eight corners of the pseudo-cube, many different cage diastereomers are possible. Each of the six tetra-aniline subcomponents investigated in this work assembled with zinc(II) and 2-formylpyridine in acetonitrile into a single Zn8L6 pseudo-cube diastereomer, however. Each product corresponded to one of four diastereomeric configurations, with T, T-h, S-6 or D-3 symmetry. The preferred diastereomer for a given tetra-aniline subcomponent was shown to be dependent on its aspect ratio and conformational flexibility. Analysis of computationally modeled individual faces or whole pseudo-cubes provided insight as to why the observed diastereomers were favored.
Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn8L6 Self-Assembled Structures / Davies, Jack A.; Tarzia, Andrew; Ronson, Tanya K.; Auras, Florian; Jelfs, Kim E.; Nitschke, Jonathan R.. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 62:10(2023). [10.1002/anie.202217987]
Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn8L6 Self-Assembled Structures
Andrew Tarzia;
2023
Abstract
We derive design principles for the assembly of rectangular tetramines into Zn8L6 pseudo-cubic coordination cages. Because of the rectangular, as opposed to square, geometry of the ligand panels, and the possibility of either Delta or ? handedness of each metal center at the eight corners of the pseudo-cube, many different cage diastereomers are possible. Each of the six tetra-aniline subcomponents investigated in this work assembled with zinc(II) and 2-formylpyridine in acetonitrile into a single Zn8L6 pseudo-cube diastereomer, however. Each product corresponded to one of four diastereomeric configurations, with T, T-h, S-6 or D-3 symmetry. The preferred diastereomer for a given tetra-aniline subcomponent was shown to be dependent on its aspect ratio and conformational flexibility. Analysis of computationally modeled individual faces or whole pseudo-cubes provided insight as to why the observed diastereomers were favored.File | Dimensione | Formato | |
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https://hdl.handle.net/11583/2981637