NMR crystallographic journey from light to heavy atoms of mercury(II)-DOTAM complexes and extraction of related structural parameters
The result's identifiers
Result code in 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>
Alternative codes found
RIV/00216224:14740/25:00142310 RIV/00216208:11310/25:10504818
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
NMR crystallographic journey from light to heavy atoms of mercury(II)-DOTAM complexes and extraction of related structural parameters
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
64
Issue of the periodical within the volume
42
Country of publishing house
US - UNITED STATES
Number of pages
15
Pages from-to
21130-21144
UT code for WoS article
001595297000001
EID of the result in the Scopus database
2-s2.0-105019932349