Guest capture and release are important properties of self-assembling nanostructures. Over time, a significant fraction of guests might engage in short-lived states with different symmetry and stereoselectivity and transit frequently between multiple environments, thereby escaping common spectroscopy techniques. Here, we investigate the cavity of an iron-based metal organic polyhedron (Fe-MOP) using spin-hyperpolarized ¹²⁹Xe Chemical Exchange Saturation Transfer (hyper-CEST) NMR. We report strong signals unknown from previous studies that persist under different perturbations. On-the-fly delivery of hyperpolarized gas yields CEST signatures that reflect different Xe exchange kinetics from multiple environments. Dilute pools with ~ 10⁴-fold lower spin numbers than reported for directly detected hyperpolarized nuclei are readily detected due to efficient guest turnover. The system is further probed by instantaneous and medium timescale perturbations. Computational modeling indicates that these signals originate likely from Xe bound to three Fe-MOP diastereomers (T, C₃, S₄). The symmetry thus induces steric effects with aperture size changes that tunes selective spin manipulation as it is employed in CEST MRI agents and, potentially, impacts other processes occurring on the millisecond time scale.

Transition metal complexes can possess a large magnetic susceptibility anisotropy, facilitating applications such as paramagnetic tags or shift agents in nuclear magnetic resonance (NMR) spectroscopy. Due to its g-shift and zero-field splitting (ZFS) we demonstrate on a Co(II) clathrochelate with an aliphatic 16-carbon chain, a modern approach for ab initio calculation of paramagnetic susceptibility. Due to its large anisotropy, large linear dimension but relatively low number of atoms, the chosen complex is especially well-suited for testing the long-range point-dipole approximation (PDA) for the pseudocontact shifts (PCSs) of paramagnetic NMR. A static structure of the complex is used to compare the limiting long-distance PDA with full first-principles quantum-mechanical calculation. A non-symmetric formula for the magnetic susceptibility tensor is necessary to be consistent with the latter. Comparison with experimental shifts is performed by conformational averaging over the chain dynamics using Monte Carlo simulation. We observe satisfactory accuracy from the rudimentary simulation and, more importantly, demonstrate the fast applicability of the ab initio PDA.

Ni²⁺(aq) has been used for many decades as a model system for paramagnetic nuclear magnetic resonance (pNMR) relaxation studies. More recently, its magnetic properties and also nuclear magnetic relaxation rates have been studied computationally. We have calculated electron paramagnetic resonance and NMR parameters using quantum-mechanical (QM) computation of molecular dynamics snapshots, obtained using a polarizable empirical force field. Statistical averages of hyperfine coupling, g- and zero-field splitting tensors, as well as the pNMR shielding terms, are compared to the available experimental and computational data. In accordance with our previous work, the isotropic hyperfine coupling as well as nuclear shielding values agree well with experimental measurements for the ¹⁷O nuclei of water molecules in the first solvation shell of the nickel ion, whereas larger deviations are found for ¹H centers. We report, for the first time, the Curie-type contribution to the pNMR relaxation rate using QM calculations together with Redfield relaxation theory. The Curie relaxation mechanism is analogous to chemical shift anisotropy relaxation, well-known in diamagnetic NMR. Due to the predominance of other types of paramagnetic relaxation mechanisms for this system, it is possible to extract the Curie term only computationally. The Curie mechanism alone would result in around 16 and 20 s⁻¹ of relaxation rates (R₁ and R₂ respectively) for the ¹H nuclei of water molecules bonded to the Ni²⁺ center, in a magnetic field of 11.7 T. The corresponding ¹⁷O relaxation rates are around 33 and 38 s⁻¹. We also report the Curie contribution to the relaxation rate for molecules beyond the first solvation shell in a 1 M solution of Ni²⁺ in water.

We exploited ¹²⁹Xe NMR to investigate xenon gas uptake and dynamics in a porous liquid formed by dissolving porous organic cages in a cavity-excluded solvent. Quantitative ¹²⁹Xe NMR shows that when the amount of xenon added to the sample is lower than the amount of cages present (subsaturation), the porous liquid absorbs almost all xenon atoms from the gas phase, with 30% of the cages occupied with a Xe atom. A simple two-site exchange model enables an estimate of the chemical shift of ¹²⁹Xe in the cages, which is in good agreement with the value provided by first-principles modeling. T₂ relaxation times allow the determination of the exchange rate of Xe between the solvent and cage sites as well as the activation energies of the exchange. The ¹²⁹Xe NMR analysis also enables determination of the free energy of confinement, and it shows that Xe binding is predominantly enthalpy-driven.

Developed multi-step computational protocol successfully models the¹³C NMR shielding tensor of carbonate in paramagnetic Mg_2−xNi_xAl-LDH.