Dataset curated
- DOI:
- https://doi.org/10.34804/supra.20210928237
- Title:
- Ammonium Complexes of Orthoester Cryptands Are Inherently Dynamic and Adaptive
- Description:
- Fluxional chemical species such as bullvalene have been a valuable source of inspiration and fundamental insight into the nature of chemical bonds. A supramolecular analogue of bullvalene, i.e., a “fluxional host–guest system”, in which the ensemble of a well-defined host and guest is engaged in continuous, degenerate constitutional rearrangements, is still elusive, however. Here, we report experimental and computational evidence for guest-induced dynamic covalent rearrangements in the ammonium complexes of self-assembled orthoester cryptands. This unique behavior is made possible by the ammonium guest playing a dual role: it is sufficiently acidic to initiate dynamic covalent exchange reactions at the orthoester bridgeheads, and as a hydrogen bond donor it acts as a supramolecular template, governing the outcome of a multitude of possible intra- and intermolecular rearrangement reactions. One particularly striking example of inherent dynamic behavior was observed in host–guest complex [NH4+⊂o-Me2-2.1.1], which spontaneously rearranged into the larger and thermodynamically more stable complex [NH4+⊂o-Me2-2.2.1], even though this process led to the formation of poor host o-Me2-1.1.1 as a consequence of the excess of one subcomponent (diethylene glycol; “1” in our nomenclature). These inherently adaptive host–guest networks represent a unique platform for exploring the interrelationship between kinetic and thermodynamic stability. For instance, as a result of optimal NH4+ binding, complex [NH4+⊂o-Me2-2.2.1] was found to be thermodynamically stable (negligible intermolecular rearrangements over weeks), whereas computational studies indicate that the compound is far from kinetically stable (intramolecular rearrangements).
| Citation: |
O. Shyshov, M. von Delius, X. Wang, C. Jäger, M. Hanževački, SupraBank 2024, Ammonium Complexes of Orthoester Cryptands Are Inherently Dynamic and Adaptive (dataset). https://doi.org/10.34804/supra.20210928237 |
| Link: | https://doi.org/10.34804/supra.20210928237 |
| Export: | BibTex | RIS | EndNote |
| Views | Downloads | Citations |
|---|---|---|
| 4472 | 0 | 0 |
| Citation: |
X. Wang, O. Shyshov, M. Hanževački, C. M. Jäger, M. von Delius, J. Am. Chem. Soc. 2019, 141, 8868–8876. |
| Link: | https://doi.org/10.1021/jacs.9b01350 |
| Export: | BibTex | RIS | EndNote | |
- Creators:
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Xiang Wang
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Oleksandr Shyshov
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Marko Hanževački
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Christof Jäger
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Max von Delius
- Contributers:
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Oleksandr Shyshov
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