Complexes of macrocyclic ligands are routinely used as MRI contrast agents and radionuclide carriers for PET and SPECT diagnostics and radiotherapy. This study explores the structural and electronic environments of two materials containing [Hg(dotam)]2+ cations, using an integrated approach combining single-crystal X-ray diffraction (SC-XRD), multinuclear solid-state magnetic resonance (ssNMR) spectroscopy (13C, 15N, 199Hg), and relativistic density functional theory (DFT) calculations. SC-XRD revealed distinct coordination motifs, including octa- and heptacoordinated [Hg(dotam)]2+ cations. Scalar and spin-orbit relativistic DFT computations accurately reproduced 13C and 15N chemical shifts, with a root-mean-square deviation of ∼0.7 ppm for 13C and ∼4.8 ppm for 15N, highlighting the importance of relativistic heavy atom effects. For 199Hg NMR, relativistic cluster-based methods (ADF/ReSpect) outperformed nonrelativistic approaches. An empirical regression model (χ̅) linked 199Hg shifts to the coordination number (CN) and averaged donor electronegativity (χ̅) (R2 = 0.86), enabling rapid structural inference. The isotropic 199Hg shift correlates with the charge on the Hg atom, influencing the p-type frontier molecular orbitals and their paramagnetic contributions to NMR shielding. This work highlights the potential of 199Hg NMR as a structural descriptor and offers a strategy for NMR crystallography involving heavy elements with possible implications for catalysis, ionic liquids, and Hg-based pharmaceuticals.

CEITEC Central European Institute of Technology Masaryk University Kamenice 753 5 62500 Brno Czechia

Department of Chemistry and Biomolecular Sciences University of Ottawa Ottawa Ontario K1N 6N5 Canada

Department of Chemistry Faculty of Science Masaryk University Kamenice 753 5 62500 Brno Czechia

Department of Inorganic Chemistry Faculty of Science Charles University Hlavova 2030 8 128 40 Prague 2 Czechia

Institute of Macromolecular Chemistry Czech Academy of Sciences Heyrovského Náměstí 2 162 00 Prague 6 Czechia

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