Chemical shifts present crucial information about an NMR spectrum. They show the influence of the chemical environment on the nuclei being probed. Relativistic effects caused by the presence of an atom of a heavy element in a compound can appreciably, even drastically, alter the NMR shifts of the nearby nuclei. A fundamental understanding of such relativistic effects on NMR shifts is important in many branches of chemical and physical science. This review provides a comprehensive overview of the tools, concepts, and periodic trends pertaining to the shielding effects by a neighboring heavy atom in diamagnetic systems, with particular emphasis on the "spin-orbit heavy-atom effect on the light-atom" NMR shift (SO-HALA effect). The analyses and tools described in this review provide guidelines to help NMR spectroscopists and computational chemists estimate the ranges of the NMR shifts for an unknown compound, identify intermediates in catalytic and other processes, analyze conformational aspects and intermolecular interactions, and predict trends in series of compounds throughout the Periodic Table. The present review provides a current snapshot of this important subfield of NMR spectroscopy and a basis and framework for including future findings in the field.

CEITEC Central European Institute of Technology Masaryk University Kamenice 5 CZ 62500 Brno Czechia

Centre of Polymer Systems Tomas Bata University in Zlı́n tř Tomáše Bati 5678 CZ 76001 Zlı́n Czechia

Department of Chemistry Faculty of Science Masaryk University Kamenice 5 CZ 62500 Brno Czechia

Institute of Chemistry Technische Universität Berlin Strasse des 17 Juni 135 D 10623 Berlin Germany

Institute of Inorganic Chemistry Slovak Academy of Sciences Dúbravská cesta 9 SK 84536 Bratislava Slovakia

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo nám 2 CZ 16610 Prague Czechia

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