Probing a Hydrogen-π Interaction Involving a Trapped Water Molecule in the Solid State

The detection and characterization of trapped water molecules in chemical entities and biomacromolecules remains a challenging task for solid materials. We herein present proton-detected solid-state Nuclear Magnetic Resonance (NMR) experiments at 100 kHz magic-angle spinning and at high static magnetic-field strengths (28.2 T) enabling the detection of a single water molecule fixed in the calix[4]arene cavity of a lanthanide complex by a combination of three types of non-covalent interactions. The water proton resonances are detected at a chemical-shift value close to zero ppm, which we further confirm by quantum-chemical calculations. Density Functional Theory calculations pinpoint to the sensitivity of the proton chemical-shift value for hydrogen-pi interactions. Our study highlights how proton-detected solid-state NMR is turning into the method-of-choice in probing weak non-covalent interactions driving a whole branch of molecular-recognition events in chemistry and biology.

Automated summary

In this study, proton-detected solid-state Nuclear Magnetic Resonance (NMR) experiments were used to detect a single water molecule trapped in a lanthanide complex by analyzing three types of non-covalent interactions. The water proton resonances were detected at a chemical-shift value close to zero ppm, which was further confirmed by quantum-chemical calculations. Density Functional Theory calculations revealed the sensitivity of the proton chemical-shift value for hydrogen-pi interactions. This study highlights the importance of proton-detected solid-state NMR in probing weak non-covalent interactions in molecular recognition events in chemistry and biology.