Publication details
Controlling Chemical Dynamics of Molecular Assemblies through Nanoconfinement: o-Nitrosocumene@Pd Nanocage
| Authors | |
|---|---|
| Year of publication | 2026 |
| Type | Peer-reviewed scientific article |
| Magazine / Source | THE JOURNAL OF ORGANIC CHEMISTRY |
| MU Faculty or unit | |
| Citation | |
| web | DOI: 10.1021/acs.joc.6c00239 |
| Doi | https://doi.org/10.1021/acs.joc.6c00239 |
| Keywords | NMR spectroscopy; palladium nanocage; exchange spectroscopy; metal; isomerism; dft calculation; NMR; chemical shift |
| Attached files | |
| Description | The change in chemical dynamics of confined ortho-nitrosocumene (o-NC), as observed by 1H NMR spectroscopy, illustrates the power of nanoconfinement to alter reaction mechanisms from those observed in isotropic solutions where molecules have more freedom. When o-NC molecules that exist as a dynamic mixture of monomer (M), covalent dimers (D), and supramolecular aggregates (A) are provided a choice of being free in water or confined within anorganometallic cage (Pd nanocage, PdNC), they prefer the latter. The confinement significantly alters the molecular distribution such that A no longer exists, and new equilibria among M and Z/E isomers of D are stablished within the nanocage and with components in the aqueous exterior. The change in equilibrium distribution of guest components demonstrates how the o-NC molecular forms of A, M, and D depend not only on concentration and temperature but also on the microenvironment surrounding the molecules. Temperature-dependent NMR and exchange spectroscopy (EXSY) with various mixing times are used to explore the M ? D equilibrium and the DZ ? DE interchange within the PdNC host. Nanoconfinement in the cage influences the dynamic interplay of dissociation, rotation, translation, and recombination events in these processes. Strikingly, the previously unreported DZ-to-DE exchange bypassing splitting to free M is enabled by entropy control in the nanoreactor. |
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