NMR crystallographic journey from light to heavy atoms of mercury(II)-DOTAM complexes and extraction of related structural parameters

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F25%3A00640869" target="_blank" >RIV/61389013:_____/25:00640869 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14740/25:00142310 RIV/00216208:11310/25:10504818

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c03503" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c03503</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5c03503" target="_blank" >10.1021/acs.inorgchem.5c03503</a>

Jazyk výsledku

angličtina

Název v původním jazyce

NMR crystallographic journey from light to heavy atoms of mercury(II)-DOTAM complexes and extraction of related structural parameters

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

NMR crystallographic journey from light to heavy atoms of mercury(II)-DOTAM complexes and extraction of related structural parameters

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

42

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

21130-21144

Kód UT WoS článku

001595297000001

EID výsledku v databázi Scopus

2-s2.0-105019932349