NMR Crystallographic Journey from Light to Heavy Atoms of
Mercury(II)-DOTAM Complexes and Extraction of Related
Structural Parameters

J 2025

NMR Crystallographic Journey from Light to Heavy Atoms of Mercury(II)-DOTAM Complexes and Extraction of Related Structural Parameters

OBUCH, Jakub; Jan NOVOTNÝ; Jiří CZERNEK; Ivana CÍSAŘOVÁ; Petr HERMANN et al.

Základní údaje

Originální název

NMR Crystallographic Journey from Light to Heavy Atoms of Mercury(II)-DOTAM Complexes and Extraction of Related Structural Parameters

Autoři

OBUCH, Jakub; Jan NOVOTNÝ; Jiří CZERNEK; Ivana CÍSAŘOVÁ; Petr HERMANN; Radek MAREK ; David L. BRYCE; Libor KOBERA a Jiří BRUS

Vydání

Inorganic Chemistry, American Chemical Society, 2025, 0020-1669

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/acs.inorgchem.5c03503

Impakt faktor

Impact factor: 4.700 v roce 2024

Označené pro přenos do RIV

Ano

Organizační jednotka

Středoevropský technologický institut

Klíčová slova anglicky

NMR spectroscopy; DFT; mercury; HALA effect; NMR shift

Štítky

14313010, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 3. 3. 2026 08:59, Mgr. Eva Dubská

Anotace

V originále

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.

Návaznosti

EH22_008/0004607, projekt VaV

Název: Nové technologie pro translační výzkum ve farmaceutických vědách /NETPHARM

GA24-10760S, projekt VaV

Název: Relativistické spin-orbitální efekty v molekulární struktuře a NMR spektroskopii

Investor: Grantová agentura ČR, Relativistické spin-orbitální efekty v molekulární struktuře a NMR spektroskopii

90254, velká výzkumná infrastruktura

Název: e-INFRA CZ II

90255, velká výzkumná infrastruktura

Název: ELIXIR CZ III

Citovat

OBUCH, Jakub; Jan NOVOTNÝ; Jiří CZERNEK; Ivana CÍSAŘOVÁ; Petr HERMANN; Radek MAREK; David L. BRYCE; Libor KOBERA a Jiří BRUS. NMR Crystallographic Journey from Light to Heavy Atoms of Mercury(II)-DOTAM Complexes and Extraction of Related Structural Parameters. Inorganic Chemistry. American Chemical Society, 2025, roč. 64, č. 42, s. 21130-21144. ISSN 0020-1669. Dostupné z: https://doi.org/10.1021/acs.inorgchem.5c03503.

@article{2526622,
   author = {Obuch, Jakub and Novotný, Jan and Czernek, Jiří and Císařová, Ivana and Hermann, Petr and Marek, Radek and Bryce, David L. and Kobera, Libor and Brus, Jiří},
   article_number = {42},
   doi = {https://doi.org/10.1021/acs.inorgchem.5c03503},
   keywords = {NMR spectroscopy; DFT; mercury; HALA effect; NMR shift},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {NMR Crystallographic Journey from Light to Heavy Atoms of Mercury(II)-DOTAM Complexes and Extraction of Related Structural Parameters},
   url = {https://doi.org/10.1021/acs.inorgchem.5c03503},
   volume = {64},
   year = {2025}
}

TY  - JOUR
ID  - 2526622
AU  - Obuch, Jakub - Novotný, Jan - Czernek, Jiří - Císařová, Ivana - Hermann, Petr - Marek, Radek - Bryce, David L. - Kobera, Libor - Brus, Jiří
PY  - 2025
TI  - NMR Crystallographic Journey from Light to Heavy Atoms of Mercury(II)-DOTAM Complexes and Extraction of Related Structural Parameters
JF  - Inorganic Chemistry
VL  - 64
IS  - 42
SP  - 21130-21144
EP  - 21130-21144
PB  - American Chemical Society
SN  - 00201669
KW  - NMR spectroscopy
KW  - DFT
KW  - mercury
KW  - HALA effect
KW  - NMR shift
UR  - https://doi.org/10.1021/acs.inorgchem.5c03503
N2  - 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.
ER  -

OBUCH, Jakub; Jan NOVOTNÝ; Jiří CZERNEK; Ivana CÍSAŘOVÁ; Petr HERMANN; Radek MAREK; David L. BRYCE; Libor KOBERA a Jiří BRUS. NMR Crystallographic Journey from Light to Heavy Atoms of Mercury(II)-DOTAM Complexes and Extraction of Related Structural Parameters. \textit{Inorganic Chemistry}. American Chemical Society, 2025, roč.~64, č.~42, s.~21130-21144. ISSN~0020-1669. Dostupné z: https://doi.org/10.1021/acs.inorgchem.5c03503.

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