Subtle Ligand Modification Inverts Guest Binding Hierarchy in M$^{II}$$_{8}$L$_{6}$ Supramolecular Cubes
Publication Date
2016-05-23Journal Title
Journal of the American Chemical Society
ISSN
0002-7863
Publisher
American Chemical Society
Volume
138
Pages
7264-7267
Language
English
Type
Article
This Version
VoR
Metadata
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Ramsay, W. J., Rizzuto, F., Ronson, T., Caprice, K., & Nitschke, J. (2016). Subtle Ligand Modification Inverts Guest Binding Hierarchy in M$^{II}$$_{8}$L$_{6}$ Supramolecular Cubes. Journal of the American Chemical Society, 138 7264-7267. https://doi.org/10.1021/jacs.6b03858
Abstract
Zinc(II), a dimolybdenum(II) paddlewheel tetramine A, and 2-formylpyridine self-assembled to generate a cubic Zn$^{II}$$_{8}$(L$^{A}$)$_{6}$ assembly. The paddlewheel faces of this assembly exhibited two distinct conformations, whereas the analogous Fe$^{II}$$_{8}$(L$^{A}$)$_{6}$ framework displayed no such perturbation to its structure. This variation in behavior is attributed to the subtle difference in ligand rotational freedom between the Zn$^{II}$- and Fe$^{II}$-cornered cubes. The incorporation of a fluorinated Mo$^{II}$$_{2}$ paddlewheel, B, into analogous Zn$^{II}$$_{8}$(L$^{B}$)$_{6}$ and Fe$^{II}$$_{8}$(L$^{B}$)$_{6}$ structures resulted in changes to the rotational dynamics of the ligands. These differing dynamics perturbed the energies of the frontier orbitals of these structures, as determined through spectroscopic and electrochemical methods. The result of these perturbations was an inversion of the halide binding preference of the Zn$^{II}$$_{8}$(L$^{B}$)$_{6}$ host as compared to its Zn$^{II}$$_{8}$(L$^{A}$)$_{6}$ congener, whereas the Fe$^{II}$$_{8}$(L$^{B}$)$_{6}$ host maintained a similar binding hierarchy to Fe$^{II}$$_{8}$(L$^{A}$)$_{6}$.
Sponsorship
Seventh Framework Programme
Funder references
EPSRC (EP/K039520/1)
EPSRC (EP/M008258/1)
Embargo Lift Date
2100-01-01
Identifiers
External DOI: https://doi.org/10.1021/jacs.6b03858
This record's URL: https://www.repository.cam.ac.uk/handle/1810/256411
Rights
Attribution 4.0 International, Attribution 4.0 International, Attribution 4.0 International, Attribution 4.0 International, Attribution 4.0 International
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