Understanding a Host-Guest Model System through 129Xe NMR Spectroscopic Experiments and Theoretical Studies

Gaining an understanding of the nature of host-guest interactions in supramolecular complexes involving heavy atoms is a difficult task. Described herein is a robust simulation method applied to complexes between xenon and members of a cryptophane family. The calculated chemical shift of xenon caged in a H2O2 probe, as modeled by quantum chemistry with complementary-orbital, topological, and energy-decomposition analyses, is in excellent agreement with that observed in hyperpolarized (XeNMR)-Xe-129 spectra. This approach can be extended to other van der Waals complexes involving heavy atoms.