Spectroscopically Visualizing the Evolution of Hydrogen-Bonding Interactions

Understanding chemical bond variations is the soul of chemistry as it is essential for any chemical process. The evolution of hydrogen bonds is one of the most fundamental and emblematic events during proton transfer; however, its experimental visualization remains a formidable challenge because of the transient timescales. Herein, by subtly regulating the proton-donating ability of distinct proton donors (zeolites or tungstophosphoric acid), a series of different hydrogen-bonding configurations were precisely manipulated. Then, an advanced two-dimensional (2D) heteronuclear correlation nuclear magnetic resonance (NMR) spectroscopic technique was utilized to simultaneously monitor the electronic properties of proton donors and acceptors (2-C-13-acetone or trimethylphosphine oxide) through chemical shifts. Parabolic H-1-C-13 NMR relationships combined with single-well and double-well potential energy surfaces derived from theoretical simulations quantitatively identified the hydrogen bond types and allowed the evolution of hydrogen bonds to be visualized in diverse acid-base interaction complexes during proton transfer. Our findings provide a new perspective to reveal the nature and evolution of hydrogen bonds and confirm the superiority of 2D NMR techniques in identifying the subtle distinctions of various hydrogen-bonding configurations.

Automated summary

Understanding the variations of chemical bonds is crucial for chemical processes, but visualizing them experimentally remains a challenge. In this study, different hydrogen-bonding configurations were manipulated by regulating the proton-donating ability of proton donors, and the electronic properties of proton donors and acceptors were simultaneously monitored using advanced 2D NMR spectroscopic technique. The evolution of hydrogen bonds was visualized in diverse acid-base interaction complexes during proton transfer, providing new insights into the nature and evolution of hydrogen bonds.