The red shift of the X-H stretching frequency, with a significant increase in intensity of the corresponding spectral band and a downfield chemical shift of hydrogen (deshielding) in nuclear magnetic resonance (NMR) spectroscopy, has traditionally been used as a criterion for identifying X-H···Y hydrogen bonds (HBs) where X is the hydrogen donor and Y is the acceptor. However, over the past two decades, it has become evident that certain HBs can exhibit a blue shift in the X-H stretching frequency and may also show a decrease in IR intensity, diverging from classical expectations. In this study, we investigate a wide array of HBs, encompassing both red-shifted and blue-shifted systems, as well as protonic and hydridic HB systems. We focus on understanding the underlying electronic conditions behind the reverse chemical shift effects─upfield shifts (shielding) upon HB formation, challenging the view that hydrogen bonding (H-bonding) typically leads to deshielding. We employ state-of-the-art quantum chemical methods, integrating computed NMR shielding tensors and electron deformation density, in combination with experimental NMR, to probe that phenomenon. The computational findings are thoroughly validated against experimental results. Our research confirms that shielding is also possible upon HB formation, thereby broadening the conceptual framework of H-bonding.

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo námĕstí 542 2 Prague 160 00 Czech Republic

IT4Innovations VŠB Technical University of Ostrava 17 listopadu 2172 15 Ostrava Poruba 708 00 Czech Republic

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