The Intermolecular NOE Depends on Isotope Selection: Short Range vs Long Range Behavior

J Phys Chem Lett. 2021 Sep 9;12(35):8658-8663. doi: 10.1021/acs.jpclett.1c02253. Epub 2021 Sep 2.

Abstract

The nuclear Overhauser effect (NOE) is a powerful tool in molecular structure elucidation, combining the subtle chemical shift of NMR and three-dimensional information independent of chemical connectivity. Its usage for intermolecular studies, however, is fundamentally limited by an unspecific long-ranged interaction behavior. This joint experimental and computational work shows that proper selection of interacting isotopes can overcome these limitations: Isotopes with strongly differing gyromagnetic ratios give rise to short-ranged intermolecular NOEs. In this light, existing NOE experiments need to be re-evaluated and future ones can be designed accordingly. Thus, a new chapter on intermolecular structure elucidation is opened.